Method for treating hair, comprising the application of a first agent (a) having a silane and a chromophoric compound, and a second agent (b) having a film-forming polymer

ABSTRACT

The subject of the present disclosure is a process for dyeing keratinous material, in particular human hair, comprising the following steps:
         Application of an agent (a) to the keratinous material, wherein the agent (a) comprises:       (a1) at least one organic silicon compound selected from the group of silanes having one, two or three silicon atoms, and   (a2) at least one colorant compound selected from the group of pigments and/or direct dyes, and
       Application of an agent (b) to the keratinous material, wherein the agent (b) comprises:   
       (b1) at least one film-forming polymer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371based on International Application No. PCT/EP2019/071623, filed Aug. 12,2019, which was published under PCT Article 21(2) and which claimspriority to German Application No. 10 2018 218 634.0, filed Oct. 31,2018, which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The subject of the present application is a method for treatingkeratinous material, in particular human hair, which comprises theapplication of two agents (a) and (b). The agent (a) is exemplified byits content of at least one organic silicon compound (a1) and at leastone coloring compound (a2). The agent (b) contains at least onefilm-forming polymer.

A further subject of this application is a multi-component packagingunit (kit-of-parts) for dyeing keratinous material, in particular humanhair, which comprises separately prepared at least three agents (a′),(a″) and (b). Agents (a′) and (a″) can be used to prepare the agent (a)used in the process described above.

BACKGROUND

The change in shape and color of keratin fibers, especially hair, is animportant area of modern cosmetics. To change the hair color, the expertknows various coloring systems depending on coloring requirements.Oxidation dyes are usually used for permanent, intensive dyeing's withgood fastness properties and good grey coverage. Such dyes usuallycontain oxidation dye precursors, so-called developer components andcoupler components, which form the actual dyes with one another underthe influence of oxidizing agents, such as hydrogen peroxide. Oxidationdyes are exemplified by very long-lasting dyeing results.

When direct dyes are used, ready-made dyes diffuse from the colorantinto the hair fiber. Compared to oxidative hair dyeing, the dyeing'sobtained with direct dyes have a shorter shelf life and quicker washability. Dyeing with direct dyes usually remain on the hair for a periodof between 5 and 20 washes.

The use of color pigments is known for short-term color changes on thehair and/or skin. Color pigments are generally understood to beinsoluble, coloring substances. These are present undissolved in the dyeformulation in the form of small particles and are only deposited fromthe outside on the hair fibers and/or the skin surface. Therefore, theycan usually be removed again without residue by a few washes withdetergents containing surfactants. Various products of this type areavailable on the market under the name hair mascara.

If the user wants particularly long-lasting dyeing's, the use ofoxidative dyes has so far been his only option. However, despitenumerous optimization attempts, an unpleasant ammonia or amine odorcannot be completely avoided in oxidative hair dyeing. The hair damagestill associated with the use of oxidative dyes also has a negativeeffect on the user's hair.

EP 2168633 B1 deals with the task of producing long-lasting haircolorations using pigments. The paper teaches that when the combinationof a pigment, an organic silicon compound, a film-forming polymer and asolvent is used on hair, it is possible to create colorations that areparticularly resistant to shampooing.

In the teaching disclosed in EP 2168633 B1, pigment, organic siliconcompound and polymer are either applied together to the keratin fiber,or the organic silicon compound is applied as a pretreatment agent,followed by the application of an agent containing pigment and polymer.In any case, the teaching of EP 2168633 B1 includes the jointapplication of pigment and polymer.

During the revision of the doctrine of EP 2168633 B1, its formulationshave been adjusted. It has been shown that the disadvantages of theseformulations are their still insufficient color intensities andinadequate wash fastness properties. Accordingly, the shampooingfastnesses of the colorations produced in EP 2168633 B1 still needimprovement.

BRIEF SUMMARY

Kits-of-parts and processes for dyeing keratinous material are provided.In an embodiment, a process for dyeing keratinous material comprisingthe following steps:

-   -   applying an agent (a) to the keratinous material, wherein the        agent (a) comprises:    -   (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   applying an agent (b) to the keratinous material, wherein the        agent (b) comprises:    -   (b1) at least one film-forming polymer.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and isnot intended to limit the disclosure or the application and uses of thesubject matter as described herein. Furthermore, there is no intentionto be bound by any theory presented in the preceding background or thefollowing detailed description.

The purpose of the present intention was to provide a dyeing system withfastness properties comparable to those of oxidative dyeing. Inparticular, the color intensities and wash fastnesses should beoutstanding, but the use of the oxidation dye precursors normally usedfor this purpose should be avoided. A technology was sought that wouldenable colorant compounds known from the prior art (such as pigments anddirect-acting dyes) to be fixed in an extremely durable manner tokeratin materials, especially hair. Even after multiple washes (such ashair washes), the colorant compounds placed on the keratin materialsshould not detach from the keratin material.

Surprisingly, it has now been found that the task can be excellentlysolved if keratinous materials, in particular human hair, are treated ordyed by a process comprising the successive application of two agents(a) and (b). Here, the first agent (a) comprises at least one organicsilicon compound selected from the group of silanes having one, two orthree silicon atoms, and further comprises at least one color-impartingcompound. In the medium (a), the organic silicon compound and thecolorant compound are thus prepared together. The second agent (b)comprises at least one film-forming polymer.

A first object of the present disclosure is a method for coloringkeratinous material, in particular human hair, comprising the followingsteps:

-   -   Application of an agent (a) to the keratinous material, wherein        the agent (a) comprises:        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   Application of an agent (b) to the keratinous material, wherein        the agent (b) comprises:        (b1) at least one film-forming polymer.

In the work leading to the present invention, it has been found that thepreferential successive application of agents (a) and (b) enables theproduction of very stable and washfast dyeing's on the keratinmaterials. Without being limited to this theory, it is suspected in thiscontext that the joint application of organic silicone compound (a1) andcolor-imparting compound (a2) leads to the formation of a particularlyresistant first film on the keratin material. With the application ofthe second agent (b), the film-forming polymer (b1) is now deposited onthis first layer in the form of a further film.

Due to this special type of packaging—i.e., the joint application ofsilane (a1) and colorant compound (a2) and separate application of thefilm-forming polymer (b1)—the multilayer film system produced in thisway exhibited improved resistance to external influences. In this way,the colorant compounds (a2) were permanently fixed to the keratinmaterial, so that extremely washfast colorations with good resistance toshampooing could be obtained.

Process for Dyeing Keratinous Material

Keratinous material includes hair, skin, nails (such as fingernailsand/or toenails). Wool, furs, and feathers also fall under thedefinition of keratinous material. Preferably, keratinous material isunderstood to be human hair, human skin, and human nails, especiallyfingernails and toenails. Keratinous material is understood to be humanhair.

Agent (a) and (b)

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous material, in particular human hair. The two agents (a)and (b) are different.

In other words, a first object of the present disclosure is a method fortreating keratinous material, in particular human hair, comprising thefollowing steps:

-   -   Application of an agent (a) to the keratinous material, wherein        the agent (a) comprises:        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   Application of an agent (b) to the keratinous material, wherein        the agent (b) comprises:        (b1) at least one film-forming polymer,        where the two agents (a) and (b) are different.

Agent (a)

Preferably, the composition (a) contains the ingredients (a1) and (a2)essential to the present disclosure in a cosmetic carrier, particularlypreferably in an aqueous or aqueous-alcoholic cosmetic carrier. Thiscosmetic carrier can be liquid, gel or cream.

Pasty, solid or powdery cosmetic carriers can also be used for thepreparation of agent (a). To hair treatment, in particular haircoloring, such carriers are, for example, creams, emulsions, gels, oralso surfactant-containing foaming solutions, such as shampoos, foamaerosols, foam formulations or other preparations suitable forapplication to the hair.

Preferably, the cosmetic carrier contains—based on its weight—at least2% by weight of water. Further preferably, the water content is above10% by weight, still further preferably above 20% by weight andparticularly preferably above 40% by weight. The cosmetic carrier canalso be aqueous-alcoholic. Aqueous/alcoholic solutions in the context ofthe present disclosure are aqueous solutions containing from about 2 toabout 70% by weight of a C₁-C₄ alcohol, more particularly ethanol orisopropanol. The agents as contemplated herein may additionally containother organic solvents, such as methoxybutanol, benzyl alcohol, ethyldiglycol or 1,2-propylene glycol. Preferred are all water-solubleorganic solvents.

Organic Silicon Compounds from the Group of Silanes (a1)

As an ingredient (a1) essential to the invention, the composition (a)contains at least one organic silicon compound from the group of silaneshaving one, two or three silicon atoms.

Particularly preferably, the agent (a) contains at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, the organic silicon compound comprising one or morehydroxyl groups and/or hydrolyzable groups per molecule.

These organic silicon compounds (a1) or organic silanes contained in theagent (a) is reactive compounds.

Organic silicon compounds, alternatively called organosilicon compounds,are compounds which either have a direct silicon-carbon bond (Si—C) orin which the carbon is bonded to the silicon atom via an oxygen,nitrogen, or sulfur atom. The organic silicon compounds as contemplatedherein are compounds containing one to three silicon atoms. Organicsilicon compounds preferably contain one or two silicon atoms.

According to IUPAC rules, the term silane chemical compounds based on asilicon skeleton and hydrogen. In organic silanes, the hydrogen atomsare completely or partially replaced by organic groups such as(substituted) alkyl groups and/or alkoxy groups. In organic silanes,some of the hydrogen atoms may also be replaced by hydroxy groups.

In a particularly preferred embodiment, a method as contemplated hereinis exemplified by the application of an agent (a) to the keratinousmaterial, said agent (a) comprising at least one organic siliconcompound (a1) selected from silanes having one, two or three siliconatoms, said organic silicon compound further comprising one or morehydroxyl groups or hydrolyzable groups per molecule.

In a very particularly preferred embodiment, a process as contemplatedherein is exemplified by the application of an agent (a) to thekeratinous material, said agent (a) comprising at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, said organic silicon compound further comprising one ormore basic chemical functions and one or more hydroxyl groups orhydrolyzable groups per molecule.

This basic group or basic chemical function can be, for example, anamino group, an alkylamino group or a dialkylamino group, which ispreferably connected to a silicon atom via a linker. The basic group ispreferably an amino group, a C₁-C₆ alkylamino group or adi(C₁-C₆)alkylamino group.

The hydrolyzable group(s) is (are) preferably a C₁-C₆ alkoxy group,especially an ethoxy group or a methoxy group. It is preferred when thehydrolyzable group is directly bonded to the silicon atom. For example,if the hydrolyzable group is an ethoxy group, the organic siliconcompound preferably contains a structural unit R′R″R′″Si—O-CH2-CH3. Theresidues R′, R″ and R′″ represent the three remaining free valences ofthe silicon atom.

A particularly preferred method as contemplated herein is exemplified inthat the composition comprises (a) at least one organic silicon compoundselected from silanes having one, two or three silicon atoms, theorganic silicon compound preferably comprising one or more basicchemical functions and one or more hydroxyl groups or hydrolyzablegroups per molecule.

Very particularly good results could be obtained if the agent (a) ascontemplated herein contains at least one organic silicon compound (a1)of formula (I) and/or (II).

The compounds of formulae (I) and (II) are organic silicon compoundsselected from silanes having one, two or three silicon atoms, theorganic silicon compound comprising one or more hydroxyl groups and/orhydrolysable groups per molecule.

In another very particularly preferred embodiment, a process ascontemplated herein is exemplified in that an agent (a) is applied tothe keratinous material (or human hair), the agent (a) comprising atleast one organic silicon compound (a1) of the formula (I) and/or (II),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

-   -   R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl        group,        -   L is a linear or branched divalent C₁-C₂₀ alkylene group,    -   R₃ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₄ represents a C₁-C₆ alkyl group        -   a, stands for an integer from 1 to 3, and        -   b stands for the integer 3−a,

(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R5, R5′, R5″ independently represent a hydrogen atom or a C₁-C₆        alkyl group,    -   R6, R6′ and R6″ independently represent a C₁-C₆ alkyl group,    -   A, A′, A″, A′″ and A″″ independently of one another represent a        linear or branched divalent C₁-C₂₀ alkylene group    -   R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl        group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an        amino C₁-C₆ alkyl group or a group of formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III),

-   -   c, stands for an integer from 1 to 3,    -   d stands for the integer 3−c,    -   c′ stands for an integer from 1 to 3,    -   d′ stands for the integer 3−c′,    -   c″ stands for an integer from 1 to 3,    -   d″ stands for the integer 3−c″,    -   e stands for 0 or 1,    -   f stands for 0 or 1,    -   g stands for 0 or 1,    -   h stands for 0 or 1,    -   provided that at least one of e, f, g, and h is different from        0.

The substituents R₁, R₂, R₃, R₄, R₅, R₅′, R₅″, R₆, R₆′, R₆″, R₇, R₈, L,A, A′, A″, A′″ and A″″ in the compounds of formula (I) and (II) areexplained below as examples:

Examples of a C₁-C₆ alkyl group are the groups methyl, ethyl, propyl,isopropyl, n-butyl, s-butyl, and t-butyl, n-pentyl and n-hexyl. Propyl,ethyl, and methyl are preferred alkyl radicals. Examples of a C₂-C₆alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl,preferred C₂-C₆ alkenyl radicals are vinyl and allyl. Preferred examplesof a hydroxy C₁-C₆ alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group isparticularly preferred. Examples of an amino C₁-C₆ alkyl group are theaminomethyl group, the 2-aminoethyl group, the 3-aminopropyl group. The2-aminoethyl group is particularly preferred. Examples of a lineardivalent C₁-C₂₀ alkylene group include the methylene group (—CH₂—), theethylene group (—CH₂—CH₂—), the propylene group (—CH₂—CH₂—CH₂—) and thebutylene group (—CH₂—CH₂—CH₂—). The propylene group (—CH₂—CH₂—CH₂—) isparticularly preferred. From a chain length of 3 C atoms, divalentalkylene groups can also be branched. Examples of branched divalentC₃-C₂₀ alkylene groups are (—CH₂—CH(CH₃)—) and (—CH₂—CH(CH₃)—CH₂—).

In the organic silicon compounds of the formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

the radicals R₁ and R₂ independently of one another represent a hydrogenatom or a C₁-C₆ alkyl group. In particular, the radicals R₁ and R₂ bothrepresent a hydrogen atom.

In the middle part of the organic silicon compound is the structuralunit or the linker -L- which stands for a linear or branched, divalentC₁-C₂₀ alkylene group.

A divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachL grouping may form two bonds. One bond is from the amino group R₁R₂N tothe linker L, and the second bond is between the linker L and thesilicon atom.

Preferably, -L- represents a linear, divalent (i.e., divalent) C₁-C₂₀alkylene group. Further preferably -L- stands for a linear divalentC₁-C₆ alkylene group. Particularly preferred -L stands for a methylenegroup (—CH₂—), an ethylene group (—CH₂—CH₂—), propylene group(—CH₂—CH₂—CH₂—) or butylene (—CH₂—CH₂—CH₂—CH₂—). L stands for apropylene group (—CH₂—CH₂—CH₂—)

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

The organic silicon compounds of formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

one end of each carries the silicon-containing group—Si(OR₃)_(a)(R₄)_(b)

In the terminal structural unit —Si(OR₃)_(a)(R₄)_(b), R₃ is hydrogen orC₁-C₆ alkyl group, and R₄ is C₁-C₆ alkyl group. R₃ and R₃ independentlyof each other represent a methyl group or an ethyl group.

Here a stands for an integer from 1 to 3, and b stands for the integer3−a. If a stands for the number 3, then b is equal to 0. If a stands forthe number 2, then b is equal to 1. If a stands for the number 1, then bis equal to 2.

Particularly resistant films could be produced if the agent (a) containsat least one organic silicon compound (a1) of formula (I) in which theradicals R₃, R₄ independently of one another represent a methyl group oran ethyl group.

When using the process as contemplated herein for dyeing keratinmaterial, dyeing's with the best wash fastnesses could be obtainedanalogously when the agent (a) contains at least one organic siliconcompound of formula (I) in which the radicals R₃, R₄ independently ofone another represent a methyl group or an ethyl group.

Furthermore, dyeing's with the best wash fastness properties could beobtained if the agent as contemplated herein contains at least oneorganic silicon compound of formula (I) in which the radical arepresents the number 3. In this case the rest b stands for the number0.

In a further preferred embodiment, the agent (a) used in the process ascontemplated herein is exemplified in that it comprises at least oneorganic silicon compound (a1) of the formula (I), where

-   -   R₃, R₄ independently of one another represent a methyl group or        an ethyl group and    -   a stands for the number 3 and    -   b stands for the number 0.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) of the formula (I),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

-   -   R₁, R₂ both represent a hydrogen atom, and    -   L represents a linear, divalent C₁-C₆-alkylene group, preferably        a propylene group (—CH₂—CH₂—CH₂—) or an ethylene group        (—CH₂—CH₂—),    -   R₃ represents a hydrogen atom, an ethyl group, or a methyl        group,    -   R₄ represents a methyl group or an ethyl group,    -   a stands for the number 3 and    -   b stands for the number 0.

Organic silicon compounds of the formula (I) which are particularlysuitable for solving the problem as contemplated herein are

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) selected from the group of

-   -   (3-Aminopropyl)triethoxysilane    -   (3-Aminopropyl)trimethoxysilane    -   1-(3-Aminopropyl)silantriol    -   (2-Aminoethyl)triethoxysilane    -   (2-Aminoethyl)trimethoxysilane    -   1-(2-Aminoethyl)silantriol    -   (3-Dimethylaminopropyl)triethoxysilane    -   (3-Dimethylaminopropyl)trimethoxysilane    -   1-(3-Dimethylaminopropyl)silantriol    -   (2-Dimethylaminoethyl)triethoxysilane    -   (2-Dimethylaminoethyl)trimethoxysilane and/or    -   1-(2-Dimethylaminoethyl)silantriol.

The organic silicon compounds of formula (I) are commercially available.(3-aminopropyl)trimethoxysilane, for example, can be purchased fromSigma-Aldrich. Also (3-aminopropyl)triethoxysilane is commerciallyavailable from Sigma-Aldrich.

In a further embodiment, the composition as contemplated hereincomprises at least one organic silicon compound (a1) of the formula (II)

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II).

The organosilicon compounds of formula (II) as contemplated herein eachcarry the silicon-containing groups (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c′) at both ends.

In the central part of the molecule of formula (II) there are the groups-(A)_(e)- and —[NR₇-(A′)]_(f)-

and —[O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-. Here, each of the radicals e,f, g, and h can independently of one another stand for the number 0 or1, with the proviso that at least one of the radicals e, f, g, and h isdifferent from 0. In other words, an organic silicon compound of formula(II) as contemplated herein contains at least one grouping from thegroup of -(A)- and —[NR₇-(A′)]- and —[O-(A″)]- and —[NR₈-(A′″)]-.

In the two terminal structural units (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c), the radicals R5, R5′, R5″ independently of oneanother represent a hydrogen atom or a C₁-C₆ alkyl group. The radicalsR6, R6′ and R6″ independently represent a C₁-C₆ alkyl group.

Here a stands for an integer from 1 to 3, and d stands for the integer3−c. If c stands for the number 3, then d is equal to 0. If c stands forthe number 2, then d is equal to 1. If c stands for the number 1, then dis equal to 2.

Analogously c′ stands for a whole number from 1 to 3, and d′ stands forthe whole number 3−c′. If c′ stands for the number 3, then d′ is 0. Ifc′ stands for the number 2, then d′ is 1. If c′ stands for the number 1,then d′ is 2.

Films with the highest stability or dyes with the best wash fastnessescould be obtained when the residues c and c′ both stand for the number3. In this case d and d′ both stand for the number 0.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) of the formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R5 and R5′ independently represent a methyl group or an ethyl        group,    -   c and c′ both stand for the number 3 and    -   d and d′ both stand for the number 0.

If c and c′ are both the number 3 and d and d′ are both the number 0,the organic silicon compound of the present disclosure corresponds toformula (IIa)

(R₅O)₃Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)₃  (IIa).

The radicals e, f, g, and h can independently stand for the number 0 or1, whereby at least one radical from e, f, g, and h is different fromzero. The abbreviations e, f, g, and h thus define which of thegroupings -(A)_(e)- and [NR₇-(A′)]_(f)- and —[O-(A″)]_(g) and—[NR8-(A′″)]_(h)-are in the middle part of the organic silicon compoundof formula (II).

In this context, the presence of certain groupings has proved to beparticularly beneficial in terms of increasing washability. Particularlygood results were obtained when at least two of the residues e, f, g,and h stand for the number 1. Especially preferred e and f both standfor the number 1. Furthermore, g and h both stand for the number 0.

If e and f both stand for the number 1 and g and h both stand for thenumber 0, the organic silicon compound as contemplated hereincorresponds to formula (IIb)

(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]—Si(R₆′)_(d′)(OR₅′)_(c′)  (IIb).

The radicals A, A′, A″, A′″ and A″″ independently represent a linear orbranched divalent C₁-C₂₀ alkylene group. Preferably the radicals A, A′,A″, A′″ and A″″ independently of one another represent a linear,divalent C₁-C₂₀ alkylene group. Further preferably the radicals A, A′,A″, A′″ and A″″ independently represent a linear divalent C₁-C₆ alkylenegroup. In particular, the radicals A, A′, A″, A′″ and A″″ independentlyof one another represent a methylene group (—CH₂—), an ethylene group(—CH₂—CH₂—), a propylene group (—CH₂—CH₂—CH₂—) or a butylene group(—CH₂—CH₂—CH₂—CH₂—). In particular, the residues A, A′, A″, A′″ and A″″stand for a propylene group (—CH₂—CH₂—CH₂—).

The divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachgrouping A, A′, A″, A′″ and A″″ may form two bonds.

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

If the radical f represents the number 1, then the organic siliconcompound of formula (II) as contemplated herein contains a structuralgrouping —[NR₇-(A′)]-.

If the radical f represents the number 1, then the organic siliconcompound of formula (II) as contemplated herein contains a structuralgrouping —[NR₈-(A′″)]-.

Wherein R₇ and R₇ independently represent a hydrogen atom, a C₁-C₆ alkylgroup, a hydroxy-C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, anamino-C₁-C₆ alkyl group or a group of the formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III).

Very preferably the radicals R7 and R8 independently of one anotherrepresent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a2-alkenyl group, a 2-aminoethyl group or a grouping of the formula(III).

If the radical f represents the number 1 and the radical h representsthe number 0, the organic silicon compound as contemplated hereincontains the grouping [NR₇-(A′)] but not the grouping —[NR₈-(A′″)]. Ifthe radical R₇ now stands for a grouping of the formula (III), the agent(a) contains an organic silicone compound with 3 reactive silane groups.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) of the formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   e and f both stand for the number 1,    -   g and h both stand for the number 0,    -   A and A′ independently represent a linear, divalent C₁-C₆        alkylene group        and    -   R₇ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl        group, a 2-alkenyl group, a 2-aminoethyl group or a group of        formula (III).

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains at least one organic siliconcompound of the formula (II), where

-   -   e and f both stand for the number 1,    -   g and h both stand for the number 0,    -   A and A′ independently of one another represent a methylene        group (—CH₂—), an ethylene group (—CH₂—CH₂—) or a propylene        group (—CH₂—CH₂—CH₂),        and    -   R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl        group, a 2-alkenyl group, a 2-aminoethyl group or a group of        formula (III).

Organic silicon compounds of the formula (II) which are well suited forsolving the problem as contemplated herein are

The organic silicon compounds of formula (II) are commerciallyavailable.

Bis(trimethoxysilylpropyl)amines with the CAS number 82985-35-1 can bepurchased from Sigma-Aldrich.Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2 canbe purchased from Sigma-Aldrich, for example.N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamineis alternatively referred to asbis(3-trimethoxysilylpropyl)-N-methylamine and can be purchasedcommercially from Sigma-Aldrich or Fluorochem.3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine withthe CAS number 18784-74-2 can be purchased for example from Fluorochemor Sigma-Aldrich.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) selected from the group of

-   3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine-   3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine-   N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine-   N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine-   2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol-   2-[bis[3-(triethoxysilyl)propyl]amino]ethanol-   3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine-   3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine-   N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,-   N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,-   N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or-   N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine

In further tests, in particular dyeing tests, it has also been found tobe particularly advantageous if the agent (a) applied to the keratinousmaterial in the process as contemplated herein contains at least oneorganic silicon compound of the formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

The compounds of formula (IV) are organic silicon compounds selectedfrom silanes having one, two or three silicon atoms, the organic siliconcompound comprising one or more hydroxyl groups and/or hydrolysablegroups per molecule.

The organic silicon compound(s) of formula (IV) may also be called asilane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂, alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) of the formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains, in addition to the organicsilicon compound(s) of formula (I), at least one further organic siliconcompound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains, in addition to the organicsilicon compound(s) of formula (II), at least one further organicsilicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the composition contains (a) in addition to theorganic silicon compound(s) of formula (I) and/or (II) at least onefurther organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In the organic silicon compounds of formula (IV), the radical R₉represents a C₁-C₁₂ alkyl group. This C₁-C₁₂ alkyl group is saturatedand can be linear or branched. Preferably, R₉ represents a linear C₁-C₈alkyl group. Preferably R₉ stands for a methyl group, an ethyl group, ann-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group,an n-octyl group or an n-dodecyl group. Particularly preferably, R₉represents a methyl group, an ethyl group or an n-octyl group.

In the organic silicon compounds of formula (IV), the radical R₁₀represents a hydrogen atom or a C₁-C₆ alkyl group. R10 stands for amethyl group or an ethyl group.

In the organic silicon compounds of formula (IV), the radical Rurepresents a C₁-C₆ alkyl group. R11 stands for a methyl group or anethyl group.

Furthermore, k stands for a whole number from 1 to 3, and m stands forthe whole number 3−k. If k stands for the number 3, then m is equal to0. If k stands for the number 2, then m is equal to 1. If k stands forthe number 1, then m is equal to 2.

Particularly stable films, i.e., dyeing's with particularly good washfastness properties, could be obtained if an agent (a) containing atleast one organic silicon compound (a1) corresponding to formula (IV):in which the radical k is the number 3, was used in the process. In thiscase the rest m stands for the number 0.

Organic silicon compounds of the formula (IV) which are particularlysuitable for solving the problem as contemplated herein are

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one organic siliconcompound (a1) of formula (IV) selected from the group of

-   -   Methyltrimethoxysilane    -   Methyltriethoxysilane    -   Ethyltrimethoxysilane    -   Ethyltriethoxysilane    -   Hexyltrimethoxysilane    -   Hexyltriethoxysilane    -   Octyltrimethoxysilane    -   Octyltriethoxysilane    -   Dodecyltrimethoxysilane and/or    -   Dodecyltriethoxysilane.

The organic silicon compounds described above are reactive compounds. Inthis context, it has been found preferable if the agent (a) ascontemplated herein contains—based on the total weight of the agent(a)—one or more organic silicon compounds (a1) in a total amount ofabout 0.1 to about 20.0% by weight, preferably about 1.0 to about 15.0%by weight and particularly preferably about 2.0 to about 8.0% by weight.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains—based on the total weight ofthe agent (a)—one or more organic silicon compounds (a1) in a totalamount of about 0.1 to about 20.0% by weight, preferably about 1.0 toabout 15.0% by weight and particularly preferably about 2.0 to about8.0% by weight.

To achieve particularly good dyeing results, it is particularlyadvantageous to use the organic silicon compounds of the formula (I)and/or (II) in certain quantity ranges on average (a). Particularlypreferably, the agent (a) contains—based on the total weight of theagent (a)—one or more organic silicon compounds of the formula (I)and/or (II) in a total amount of about 0.1 to about 10.0% by weight,preferably about 0.5 to about 5.0% by weight and particularly preferablyabout 0.5 to about 3.0% by weight.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a)—based on the total weight of agent(a)—contains one or more organic silicon compounds of formula (I) and/or(II) in a total amount of about 0.1 to about 10.0% by weight, preferablyabout 0.5 to about 5.0% by weight and particularly preferably about 0.5to about 3.0% by weight.

Furthermore, it has proven to be particularly preferred if the organicsilicon compound(s) of formula (IV) is (are) also present in certainquantity ranges in average (a). Particularly preferably the agent (a)contains—based on the total weight of agent (a)—one or more organicsilicon compounds of the formula (IV) in a total amount of about 0.1 toabout 20.0% by weight, preferably about 2.0 to about 15.0% by weight andparticularly preferably about 4.0 to about 9.0% by weight.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a)—based on the total weight of agent(a)—contains one or more organic silicon compounds of formula (IV) in atotal amount of about 0.1 to about 20.0% by weight, preferably about 2.0to about 15.0% by weight and particularly preferably about 3.2 to about10.0% by weight.

In the course of the work leading to this invention, it was found thatparticularly stable and uniform films could be obtained on the keratinmaterial even if the agent (a) contained two organic silicon compoundsthat were structurally different from each other.

In another preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains at least two structurallydifferent organic silicon compounds.

In an explicitly quite particularly preferred embodiment, a process ascontemplated herein is exemplified in that an agent (a) is applied tothe keratinous material, which agent contains at least one organicsilicone compound of the formula (I) which is selected from the group of(3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, andadditionally contains at least one organic silicone compound of theformula (IV) which is selected from the group of methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a)—based on the total weight of agent(a)—contains:

-   -   from about 0.5 to about 5.0% by weight of at least one first        organic silicon compound (a1) selected from the group of        (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,        (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane,        (3-dimethylaminopropyl)trimethoxysilane,        (3-dimethylaminopropyl)triethoxysilane        (2-dimethylaminoethyl)trimethoxysilane and        (2-dimethylaminoethyl)triethoxysilane, and    -   from about 3.2 to about 10.0% by weight of at least one second        organic silicon compound (a1) selected from the group of        methyltrimethoxysilane, methyltriethoxysilane,        ethyltrimethoxysilane, ethyltriethoxysilane,        octyltrimethoxysilane, octyltriethoxysilane,        dodecyltrimethoxysilane and dodecyltriethoxysilane.

In this version, the agent contains (a) one or more organic siliconcompounds of a first group in a total amount of about 0.5 to about 3.0%by weight. The organic silicon compounds of this first group areselected from the group of (3-aminopropyl)trimethoxysilane,(3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane,(2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane,(3-dimethylaminopropyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane and/or(2-dimethylaminoethyl)triethoxysilane.

In this version, the agent contains (a) one or more organic siliconcompounds of a second group in a total amount of about 3.2 to about10.0% by weight. The organic silicon compounds of this second group areselected from the group of methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilaneand/or dodecyltriethoxysilane.

Color-Forming Compounds (a2)

When agent (a) is applied to the keratin material, the organic siliconcompound(s) (a1) comprising one or more hydroxyl groups or hydrolyzablegroups per molecule are first hydrolyzed and oligomerized or polymerizedin the presence of the water. The resulting hydrolysis products oroligomers have a particularly high affinity to the surface of theKeratin material. The simultaneous presence of the colorant compounds(a2) in the agent (a) integrates them into the resulting oligomers orpolymers to form a colored film on the keratin material. Following theapplication of agent (a), agent (b) is now applied, whereby thefilm-forming polymers (b1) contained in this agent (b) are deposited onthe keratinous material in the form of a second film. The successiveapplication of agents (a) and (b) thus creates a layering of severalfilms that is particularly resistant to external influences. Thecolorant compounds trapped in these resistant films exhibit extremelygood wash fastness.

As an essential component (a2) of the invention, the agent (a) used inthe process as contemplated herein therefore contains at least onecolorant compound from the group of pigments and/or direct dyes.

The use of pigments has proved to be particularly preferable in thiscontext.

In another very particularly preferred embodiment, a process ascontemplated herein is exemplified in that the agent (a) comprises atleast one colorant compound (a2) from the group of pigments.

Pigments within the meaning of the present disclosure are coloringcompounds which have a solubility in water at 25° C. of less than 0.5g/L, preferably less than 0.1 g/L, even more preferably less than 0.05g/L. Water solubility can be determined, for example, by the methoddescribed below: 0.5 g of the pigment are weighed in a beaker. Astir-fish is added. Then one liter of distilled water is added. Thismixture is heated to 25° C. for one hour while stirring on a magneticstirrer. If undissolved components of the pigment are still visible inthe mixture after this period, the solubility of the pigment is below0.5 g/L. If the pigment-water mixture cannot be assessed visually due tothe high intensity of the possibly finely dispersed pigment, the mixtureis filtered. If a proportion of undissolved pigments remains on thefilter paper, the solubility of the pigment is below 0.5 g/L.

Suitable color pigments can be of inorganic and/or organic origin.

In a preferred embodiment, an agent as contemplated herein isexemplified in that the agent (a) contains at least one colorantcompound (a2) from the group of inorganic and/or organic pigments.

Preferred color pigments are selected from synthetic or naturalinorganic pigments. Inorganic color pigments of natural origin can beproduced, for example, from chalk, ochre, umber, green earth, burntTerra di Siena or graphite. Furthermore, black pigments such as ironoxide black, colored pigments such as ultramarine or iron oxide red aswell as fluorescent or phosphorescent pigments can be used as inorganiccolor pigments.

Particularly suitable are colored metal oxides, hydroxides and oxidehydrates, mixed-phase pigments, sulfur-containing silicates, silicates,metal sulfides, complex metal cyanides, metal sulphates, chromatesand/or molybdates. Preferred color pigments are black iron oxide (CI77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI77289),iron blue (ferric ferrocyanides, CI77510) and/or carmine (cochineal).

As contemplated herein, colored pearlescent pigments are alsoparticularly preferred color pigments. These are usually mica- and/ormica-based and can be coated with one or more metal oxides. Mica belongsto the layer silicates. The most important representatives of thesesilicates are muscovite, phlogopite, paragonite, biotite, lepidolite andmargarite. To produce the pearlescent pigments in combination with metaloxides, the mica, mainly muscovite or phlogopite, is coated with a metaloxide.

As an alternative to natural mica, synthetic mica coated with one ormore metal oxides can also be used as pearlescent pigment. Especiallypreferred pearlescent pigments are based on natural or synthetic mica(mica) and are coated with one or more of the metal oxides mentionedabove. The color of the respective pigments can be varied by varying thelayer thickness of the metal oxide(s).

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one colorantcompound (a2) from the group of inorganic pigments selected from thegroup of colored metal oxides, metal hydroxides, metal oxide hydrates,silicates, metal sulfides, complex metal cyanides, metal sulfates,bronze pigments and/or from colored mica- or mica-based pigments coatedwith at least one metal oxide and/or a metal oxychloride.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one colorantcompound (a2) from the group of pigments selected from mica- ormica-based pigments which are reacted with one or more metal oxides fromthe group of titanium dioxide (CI 77891), black iron oxide (CI 77499),yellow iron oxide (CI 77492), red and/or brown iron oxide (CI 77491, CI77499), manganese violet (CI 77742), ultramarine (sodium aluminumsulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289), chromium oxide (CI 77288) and/or iron blue (ferric ferrocyanide,CI 77510).

Examples of particularly suitable color pigments are commerciallyavailable under the trade names Rona®, Colorona®, Xirona®, Dichrona® andTimiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® fromEckart Cosmetic Colors and Sunshine® from Sunstar.

Particularly preferred color pigments with the trade name Colorona® are,for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona PassionOrange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona PatinaSilver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470(CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA,TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona BlackstarBlue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple,Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491(IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona ImperialRed, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUMDIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold,Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRONOXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE,CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze,Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA,CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891(TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck,CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491(IRON OXIDES)

Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide),Silica, CI 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRONOXIDES, MICA, CI 77891, CI 77491 (EU)

Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891(Titanium dioxide)Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491(Iron oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Other particularly preferred color pigments with the trade name Xirona®are for example:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin OxideXirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica,Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide),Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (TitaniumDioxide), Tin Oxide.

In addition, particularly preferred color pigments with the trade nameUnipure® are for example:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica UnipureBlack LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure YellowLC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment of the process as contemplated herein, the agent(a) may also contain one or more colorant compounds from the group oforganic pigments.

The organic pigments as contemplated herein are correspondinglyinsoluble, organic dyes or color lacquers, which may be selected, forexample, from the group of nitroso, nitro-azo, xanthene, anthraquinone,isoindolinone, isoindolinone, quinacridone, perinone, perylene,diketo-pyrrolopyorrole, indigo, thioindido, dioxazine and/ortriarylmethane compounds.

Examples of particularly suitable organic pigments are carmine,quinacridone, phthalocyanine, sorghum, blue pigments with the ColorIndex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments with the Color Index numbers CI 11680, CI 11710,CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005,green pigments with the Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with the Color Index numbers CI 11725, CI 15510,CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085,CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In another particularly preferred embodiment, a process as contemplatedherein is exemplified in that the composition (a) comprises at least onecolorant compound (a2) from the group of organic pigments selected fromthe group of carmine, quinacridone, phthalocyanine, sorghum, bluepigments having the color index numbers CI 42090, CI 69800, CI 69825, CI73000, CI 74100, CI 74160, yellow pigments having the color indexnumbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI21108, CI 47000, CI 47005, green pigments with Color Index numbers CI61565, CI 61570, CI 74260, orange pigments with Color Index numbers CI11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Indexnumbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI73915 and/or CI 75470.

The organic pigment can also be a color paint. As contemplated herein,the term color varnish is understood to mean particles comprising alayer of absorbed dyes, the unit of particle and dye being insolubleunder the above conditions. The particles can, for example, be inorganicsubstrates, which can be aluminum, silica, calcium borosilate, calciumaluminum borosilicate or even aluminum.

For example, alizarin color varnish can be used.

Due to their excellent resistance to light and temperature, the use ofthe pigments in the compositions as contemplated herein is particularlypreferred. It is also preferred if the pigments used have a certainparticle size. This particle size leads on the one hand to an evendistribution of the pigments in the formed polymer film and on the otherhand avoids a rough hair or skin feeling after application of thecosmetic product. As contemplated herein, it is therefore advantageousif the at least one pigment has an average particle size D50 of fromabout 1.0 to about 50 μm, preferably about 5.0 to about 45 μm,preferably about 10 to about 40 μm, about 14 to about 30 μm. The meanparticle size D50, for example, can be determined using dynamic lightscattering (DLS).

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains—based on the total weight ofthe agent (a)—one or more pigments in a total amount of from about 0.01to about 10.0% by weight, preferably from about 0.1 to about 8.0% byweight, more preferably from about 0.2 to about 6.0% by weight and veryparticularly preferably from about 0.5 to about 4.5% by weight.

As colorant compound(s) (a2), the agents (a) used in the process ascontemplated herein may also contain one or more direct dyes.Direct-acting dyes are dyes that draw directly onto the hair and do notrequire an oxidative process to form the color. Direct dyes are usuallynitrophenylene diamines, nitroaminophenols, azo dyes, anthraquinones,triarylmethane dyes or indophenols.

The direct dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments.

Preferably, the direct dyes within the meaning of the present disclosurehave a solubility in water (760 mmHg) at 25° C. of more than 1.0 g/L.

Direct dyes can be divided into anionic, cationic, and non-ionic directdyes.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one anionic,cationic and/or nonionic direct dye as the coloring compound (a2).

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one colorantcompound (a2) from the group of anionic, nonionic, and/or cationicdirect dyes.

Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, BasicViolet 2, and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue No. 16, BasicBlue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow87, Basic Orange 31, Basic Red 51 Basic Red 76

As non-ionic direct dyes, non-ionic nitro and quinone dyes and neutralazo dyes can be used. Suitable non-ionic direct dyes are those listedunder the international designations or Trade names HC Yellow 2, HCYellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, DisperseOrange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC RedBN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1,Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds,as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)-aminophenol2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-4-nitrophenol.

In the course of the work leading to the present invention, it has beenfound that dyeing's of particularly high color intensity can be producedwith agents (a) containing at least one anionic direct dye.

In an explicitly quite particularly preferred embodiment, a process ascontemplated herein is therefore exemplified in that the agent (a)comprises at least one anionic direct dye.

Anionic direct dyes are also called acid dyes. Acid dyes are direct dyesthat have at least one carboxylic acid group (—COOH) and/or onesulphonic acid group (—SO₃H). Depending on the pH value, the protonatedforms (—COOH, —SO₃H) of the carboxylic acid or sulphonic acid groups arein equilibrium with their deprotonated forms (—OO⁻, —SO₃ ⁻— present).The proportion of protonated forms increases with decreasing pH. Ifdirect dyes are used in the form of their salts, the carboxylic acidgroups or sulphonic acid groups are present in deprotonated form and areneutralized with corresponding stoichiometric equivalents of cations tomaintain electro neutrality. Inventive acid dyes can also be used in theform of their sodium salts and/or their potassium salts.

The acid dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments. Preferably the acid dyeswithin the meaning of the present disclosure have a solubility in water(760 mmHg) at 25° C. of more than 1.0 g/L.

The alkaline earth salts (such as calcium salts and magnesium salts) oraluminum salts of acid dyes often have a lower solubility than thecorresponding alkali salts. If the solubility of these salts is below0.5 g/L (25° C., 760 mmHg), they do not fall under the definition of adirect dye.

An essential characteristic of acid dyes is their ability to formanionic charges, whereby the carboxylic acid or sulphonic acid groupsresponsible for this are usually linked to different chromophoricsystems. Suitable chromophoric systems can be found, for example, in thestructures of nitrophenylenediamines, nitroaminophenols, azo dyes,anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes,oxazine dyes and/or indophenol dyes.

In one embodiment, a process for dyeing keratinous material is thuspreferred, which is exemplified in that the composition (a) comprises atleast one anionic direct dye selected from the group ofnitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes,triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and/orindophenol dyes, the xanthene dyes, the rhodamine dyes, the oxazine dyesand/or the indophenol dyes, the dyes from the abovementioned group eachhaving at least one carboxylic acid group (—COOH), a sodium carboxylategroup (—COONa), a potassium carboxylate group (—COOK), a sulfonic acidgroup (—SO₃H), a sodium sulfonate group (—SO₃Na) and/or a potassiumsulfonate group (—SO₃K).

For example, one or more compounds from the following group can beselected as particularly well suited acid dyes: Acid Yellow 1 (D&CYellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316,COLIPA no B001), Acid Yellow 3 (COLIPA no: C 54, D&C Yellow No 10,Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), AcidYellow 17 (CI 18965), Acid Yellow 23 (COLIPA no C. 29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), AcidYellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7(2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA no C₀₁₅),Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), AcidOrange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No. 201;RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No. 1),Acid Red 14 (C.I. 14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9,Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200),Acid Red 35 (CI C.I.18065), Acid Red 51 (CI 45430, Pyrosin B,Tetraiodfluorescein, Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red106, Solar Rhodamine B, Acid Rhodamine B, Red no 106 Pontacyl BrilliantPink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red92 (COLIPA no C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, AcidViolet 43 (Jarocol Violet 43, Ext. D&C Violet no 2, C.I. 60730, COLIPAno C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), AcidBlue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blue V, CI 42051),Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133,Patent blue AE, Amidoblau AE, Erioglaucin A, CI 42090, C.I. Food Blue2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI42095), Acid Green 9 (C.I.42100), Acid Green 22 (C.I.42170), Acid Green25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50(Brilliant Acid Green BS, C.I. 44090, Acid Brilliant Green BS, E 142),Acid Black 1 (Black no 401, Naphthalene Black 10B, Amido Black 10B, CI20 470, COLIPA no B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&COrange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&CBrown 1.

For example, the water solubility of anionic direct dyes can bedetermined in the following way. 0.1 g of the anionic direct dye isplaced in a beaker. A stir-fish is added. Then add 100 ml of water. Thismixture is heated to 25° C. on a magnetic stirrer while stirring. It isstirred for 60 minutes. The aqueous mixture is then visually assessed.If there are still undissolved residues, the amount of water isincreased—for example in steps of 10 ml. Water is added until the amountof dye used is completely dissolved. If the dye-water mixture cannot beassessed visually due to the high intensity of the dye, the mixture isfiltered. If a proportion of undissolved dyes remains on the filterpaper, the solubility test is repeated with a higher quantity of water.If 0.1 g of the anionic direct dye dissolves in 100 ml water at 25° C.,the solubility of the dye is 1.0 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic aciddisodium salt and has a solubility in water of at least 40 g/L (25° C.).

Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonicacids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a watersolubility of 20 g/L (25° C.).Acid Yellow 9 is the disodium salt of8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility inwater is above 40 g/L (25° C.).Acid Yellow 23 is the trisodium salt of4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylicacid and is highly soluble in water at 25° C.Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulphonate. Its water solubility is more than 7 g/L (25° C.).Acid Red 18 is the trinatirum salt of7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has a very high-water solubility of more than 20% byweight.Acid Red 33 is the diantrium salt of5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, itssolubility in water is 2.5 g/L (25° C.).Acid Red 92 is the disodium salt of3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoicacid, whose solubility in water is indicated as greater than 10 g/L (25°C.).Acid Blue 9 is the disodium salt of2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonateand has a solubility in water of more than 20% by weight (25° C.).

A very particularly preferred method as contemplated herein is thereforeexemplified in that,

in that the composition (a) comprises at least one coloring compound(a2) from the group of anionic direct dyes selected from the group of AAcid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, AcidOrange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, AcidRed 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95,Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9,Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5,Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1,Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5,D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&CViolet 2 and/or D&C Brown 1.

The direct dye(s), in the anionic direct dyes, can be used in differentamounts in the medium (a) depending on the desired color intensity.Particularly good results were obtained when the agent (a)contains—based on its total weight—one or more direct dyes (a2) in atotal amount of from about 0.01 to about 10.0% by weight, preferablyfrom about 0.1 to about 8.0% by weight, more preferably from about 0.2to about 6.0% by weight and very particularly preferably from about 0.5to about 4.5% by weight.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) contains—based on the total weight ofthe agent (a)—one or more direct dyes (a2) in a total amount of fromabout 0.01 to about 10.0% by weight, preferably from about 0.1 to about8.0% by weight, more preferably from about 0.2 to about 6.0% by weightand very preferably from about 0.5 to about 4.5% by weight.

Silicone Polymers (a3)

In another very particularly preferred embodiment, the agent (a) used inthe process as contemplated herein additionally contains at least onesilicone polymer (a3).

Silicone polymers, which can alternatively be called silicones forshort, are understood to be poly(organo)siloxanes. Silicone polymers area group of synthetic polymers in which silicon atoms are linked viaoxygen atoms.

Silicone polymers are generally macromolecules with a molecular weightof at least 500 g/mol, preferably at least 1000 g/mol, more preferablyat least 2500 g/mol, particularly preferably at least 5000 g/mol, whichcomprise repeating organic units.

The maximum molecular weight of the silicone polymer depends on thedegree of polymerization (number of polymerized monomers) and the batchsize and is partly determined by the polymerization method. For thepurposes of the present invention, it is preferred if the maximummolecular weight of the silicone polymer is not more than 10⁷ g/mol,preferably not more than 10⁶ g/mol, and particularly preferably not morethan 10⁵ g/mol.

The silicone polymers comprise many Si—O repeating units, and the Siatoms may carry organic radicals such as alkyl groups or substitutedalkyl groups.

Corresponding to the high molecular weight of silicone polymers, theseare based on more than 10 Si—O repeat units, preferably more than 50Si—O repeat units, and more preferably more than 100 Si—O repeat units,most preferably more than 500 Si—O repeat units.

The silicone polymers (a3) contained in agent (a) are thereforedifferent from the silanes (a1) also contained in agent (a).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is exemplified in that the agentcomprises (a):(a3) at least one silicone polymer.

In the work leading to the present invention, it was found thatincorporation of the silicone polymer (a3) into the agent (a) resultedin an improvement in hair feel.

The film produced by the oligomerization or polymerization of theorganosilicon compounds (silanes) (a1) may exhibit a certain stickinessor even softness, especially when higher amounts of silanes (a1) areused, which may have a negative effect on the feel of the keratinmaterials on the one hand and on the durability of the film on theother. Without being committed to this theory, it is believed that thejoint application of the silane (a1) and the silicone polymer (a3) inthe medium (a) leads to a reaction or interaction of the two componentswith each other. When silane and silicone polymer are used together, thesilanes appear to form a film, as previously described, into which thesilicone polymers are either incorporated, or to which the siliconepolymers agglomerate. It has been found that the film formed in this wayis much more supple, flexible, durable, and less brittle.

Accordingly, it was observed that the rheological properties of the filmproduced by agent (a) could be greatly improved by the addition of atleast one silicone polymer (a3). In the presence of the siliconepolymers (a3), the film became firmer or more rigid, leaving the coloredkeratin materials with a less sticky, smoother, and more pleasingappearance. Furthermore, the higher strength of the film also hadpositive effects on the fastness properties of the keratin materials,especially on their rub fastness properties. Since the dyed films weremore resistant when in contact with combs, brushes, and textiles, theyshowed less abrasion when in contact with these items.

When certain silicone polymers (a3) were used, the advantages describedabove were particularly pronounced. It has therefore been found to beparticularly preferred if the agents (a) used in the process ascontemplated herein contain at least one alkoxy-modified siliconepolymer and/or at least one amino-modified silicone polymer (a3).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is exemplified in that the agentcomprises (a):

(a3) at least one alkoxy-modified and/or amino-modified siliconepolymer.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one alkoxy-modifiedsilicone polymer.

Alkoxy-modified silicones are silicones whose structure includes atleast one structural alkoxy unit. This structural alkoxy unit can be,for example, an alkoxy group. Alkoxy groups are understood to be C₂-C₁₀alkoxy groups. The alkoxy group may be terminal to the silicone (i.e.,present, for example, as the group —O—CH₃ or as the group —O—CH₂—CH₃).However, it is equally as contemplated herein if the alkoxy group itselfstill carries a substituent; in this case, an alkoxy modification isunderstood to be at least one grouping located on the silicone such as,for example, (—CH2-CH2-O—), (—CH2-CH2-CH2-O—), (—CH(CH3)-CH2-O—),(—CH2-CH(CH3)-CH2-O—) or (—CH2-CH2-CH2-CH2-O—). Preferably, thealkoxy-modified silicones (A) as contemplated herein carry at least onegrouping (—CH2-CH2-O—) and/or (—CH2-CH2-CH2-O—).

The alkoxy groups may be linked to the silicone either via a carbon atomor via an oxygen atom, for example, the silicones may bear thestructural units of the formula (S-a), (S-b), (S-c) and/or (S-d):

It is particularly preferred if the alkoxy-modified silicone polymer(s)(a3) carry more than one alkoxy group, i.e., if the silicone polymers(a3) are polyalkoxylated. Polyalkoxylated silicones carry as structuralunits polyoxyalkylene groups, polyoxyethylene groups (i.e., groups ofthe type [—CH₂—CH₂—O-]_(m)) and/or poloxypropylene groups (i.e., groupsof the type [—CH(CH3)-CH2-O-]_(m) and/or [—CH2-CH2-CH2-O-]_(m)).Preferably, the number of polyoxyalkylene units in the silicone polymeris at least 2. m is therefore an integer greater than or equal to 2.

Particularly preferably, the alkoxy-modified silicone (a3) is a nonionicsilicone. Non-ionic silicones carry neither positive nor negativecharges.

Very particularly suitable polyalkoxylated silicones (a3) comprise atleast one structural unit of the formula (S-I)

whereinn is an integer from about 2 to about 20, preferably an integer fromabout 4 to about 18, more preferably an integer from about 6 to about16, still more preferably an integer from about 8 to about 14, and mostpreferably the number 12.

The positions marked with an asterisk * in the above formulas representthe free valences of the corresponding bonds, whereby the bond can be toa further Si atom, a further O atom and/or a further C atom.

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is exemplified in that the agentcomprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of formula (S-I)

wherein

n is an integer from about 2 to about 20, preferably an integer fromabout 4 to about 18, more preferably an integer from about 6 to about16, still more preferably an integer from about 8 to about 14, and mostpreferably the number 12.

A preferred alkoxy-modified silicone polymer (a3) may contain, inaddition to one or more structural units of the general formula (S-I),further structural units that differ structurally from the units offormula (S-I). Particularly preferably, the alkoxy-modified siliconepolymer additionally comprises one or more dimethylsiloxane units.Depending on whether the silicone of the present disclosure is linear orbranched, it has two (in the case of a chain linear silicone) or more(in the case of a branched silicone) end groups. It has been found to beparticularly advantageous if a silicone polymer (a3) as contemplatedherein has a trimethylsilyloxy group (i.e., a group —O—Si(CH₃)₃) as endgroups in each case.

In another very particularly preferred embodiment, a process ascontemplated herein is therefore exemplified in that the agent (a)comprises at least one silicone polymer (a3) which is composed ofstructural units of the formula (S-I), the formula (S-II), the formula(S-III) and the formula (S-IV),

wherein n- independently in each structural unit (S-I)—represents ineach case an integer from about 2 to about 20, preferably an integerfrom about 4 to about 18, more preferably an integer from about 6 toabout 16, still more preferably an integer from about 8 to about 14, andmost preferably the number 12.

A silicone polymer (a3) composed of structural units of the formula(S-I), the formula (S-II), the formula (S-III) and the formula (S-IV) isunderstood in this context to mean a silicone which exclusivelypossesses (in each case one or more) structural units of the formulae(S-I), (S-II), (S-III) and (S-IV). Here, the silicone can also containdifferent structural units of the formula (S-I), each of which isdistinguished by its number n.

The positions marked with an asterisk in the structural units eachrepresent the linkage points to the other structural units. For example,a very particularly preferred silicone polymer (a3) composed ofstructural units of formula (S-I), formula (S-II), formula (S-III) andformula (S-IV) may have the following structure:

x and y are chosen here depending on the desired molecular weight of thesilicone, and n represents one of the preferred or particularlypreferred integers described above as contemplated herein.

Both low molecular weight and higher molecular weight alkoxy-modifiedsilicones can be used as silicone polymers (a3). Particularly beneficialeffects were observed for silicone polymers (a3) with a molar mass ofabout 800 to about 10 000 g/mol, preferably of about 1 000 to about 9000 g/mol, further preferably of about 2 000 to about 8 000 g/mol andespecially preferably of about 2 500 to about 5 000 g/mol.

Particularly well-suited silicone polymers include:

Abil B 8843 by the company Evonic, PEG-14 DIMETHICONEXiameter OFX 0193 Fluid by the company Dow Corning, PEG-12 Dimethicone

Furthermore, particularly good results were also obtained when an agent(a) containing an amino-modified silicone polymer (a3) was used in theprocess as contemplated herein. The amino-modified silicone polymer mayalternatively be referred to as an amino-functionalized silicone polymeror also as an aminosilicone.

In another preferred embodiment, a process as contemplated herein isexemplified in that the agent (a) comprises at least one amino-modifiedsilicone polymer.

Agent (a) may contain one or more different amino-modified siliconepolymers (a3). Such silicones can be exemplified, for example, by theformula (S-V)

M(R_(a)Q_(b)SiO_((4-a-b)/2)x)(R_(c)SiO_((4-c)/2)y)M  (S-V)

in which formula above R is a hydrocarbon or a hydrocarbon radicalhaving from 1 to about 6 carbon atoms, Q is a polar radical of thegeneral formula —R¹HZ wherein R¹ is a divalent linking group bonded tohydrogen and the radical Z composed of carbon and hydrogen atoms,carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogenatoms, and Z is an organic amino functional radical containing at leastone amino functional group; “a” takes values ranging from about 0 toabout 2, “b” takes values ranging from about 1 to about 3, “a”+“b” isless than or equal to 3, and “c” is a number ranging from about 1 toabout 3, and x is a number ranging from about 1 to about 2.000,preferably from about 3 to about 50 and most preferably from about 3 toabout 25, and y is a number in the range of from about 20 to about10,000, preferably from about 125 to about 10,000 and most preferablyfrom about 150 to about 1,000, and M is a suitable silicone end group asknown in the prior art, preferably trimethylsiloxy. Non-limitingexamples of radicals represented by R include alkyl radicals, such asmethyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl,isoamyl, hexyl, isohexyl and the like; alkenyl radicals, such as vinyl,halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkylradicals, such as cyclobutyl, cyclopentyl, cyclohexyl and the like;phenyl radicals, benzyl radicals, halohydrocarbon radicals, such as3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl,bromophenyl, chlorophenyl and the like, and sulfur-containing radicals,such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl andthe like; preferably R is an alkyl radical containing from 1 to about 6carbon atoms, and most preferably R is methyl. Examples of R¹ includemethylene, ethylene, propylene, hexamethylene, decamethylene,—CH₂CH(CH₃)CH₂—, phenylene, naphthylene,—CH₂CH₂SCH₂CH₂—, —CH₂CH₂OCH₂—,—OCH₂CH₂—, —OCH₂CH₂CH₂—CH₂CH(CH₃)C(O)OCH₂—, —(CH₂)₃CC(O)OCH₂CH₂—,—C₆H₄C₆H₄—, —C₆H₄CH₂C₆H₄—; and —(CH₂)₃C(O)SCH₂CH₂—.

Z is an organic amino functional residue containing at least one aminofunctional group. One possible formula for Z is NH(CH₂)_(z)NH₂, where zis 1 or more. Another possible formula for Z is—NH(CH₂)_(z)(CH₂)_(zz)NH, wherein both z and zz are independently 1 ormore, this structure comprising diamino ring structures, such aspiperazinyl. Z is most preferably an —NHCH₂CH₂NH₂ residue. Anotherpossible formula for Z is —N(CH₂)_(z)(CH₂)_(zz)NX₂ or —NX₂, wherein eachX of X₂ is independently selected from the group of hydrogen and alkylgroups having 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine-functional radical of the formula—CH₂CH₂CH₂NHCH₂CH₂NH₂. In the formulas, “a” takes values ranging fromabout 0 to about 2, “b” takes values ranging from about 2 to about 3,“a”+“b” is less than or equal to 3, and “c” is a number ranging fromabout 1 to about 3. The molar ratio of R_(a)Q_(b)SiO_((4-a-b)/2) unitsto R_(c)SiO_((4-c)/2) units is in the range of about 1:2 to about 1:65,preferably from about 1:5 to about 1:65 and most preferably by about1:15 to about 1:20. If one or more silicones of the above formula areused, then the various variable substituents in the above formula may bedifferent for the various silicone components present in the siliconemixture.

In a particularly preferred embodiment, a method as contemplated hereinis exemplified by the application of an agent (a) to the keratinousmaterial, wherein the agent (a) is an amino-modified silicone polymer(a3) of formula (S-VI)

R′_(a)G_(3-a)-Si(OSiG₂)_(n)-(OSiG_(b)R′_(2-b))_(m)—O—SiG_(3-a)-R′_(a)  (S-VI),

wherein:

-   -   G is —H, a phenyl group, OH, —O—CH₃, —CH₃, —O—CH₂CH₃, —CH₂CH₃,        —O—CH₂CH₂CH₃,—CH₂CH₂CH₃, —O—CH(CH₃)₂, —CH(CH₃)₂,        —O—CH₂CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, —O—CH₂CH(CH₃)₂, —CH₂CH(CH₃)₂,        —O—CH(CH₃)CH₂CH₃, CH(CH₃)CH₂CH₃, —O—C(CH₃)₃, —C(CH₃)₃.    -   a stands for a number between 0 and 3, especially 0.    -   b stands for a number between 0 and 1, especially 1,    -   m and n are numbers whose sum (m+n) is between 1 and 2000,        preferably between 50 and 150, where n preferably assumes values        from 0 to 1999 and from 49 to 149 and m preferably assumes        values from 1 to 2000, from 1 to 10,    -   R is a monovalent radical selected from        -   -Q-N(R″)—CH₂—CH₂—N(R″)₂        -   -Q-N(R″)₂        -   -Q-N⁺(R″)₃A⁻        -   -Q-N⁺H(R″)₂A⁻        -   Q-N⁺H₂(R″)A⁻        -   Q-N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,            where each Q is a chemical bond, —CH₂—, —CH₂—CH₂—,            —CH₂CH₂CH₂—, —C(CH₃)₂—, —CH₂CH₂CH₂CH₂—, —CH₂C(CH₃)₂—,            —CH(CH₃)CH₂CH₂—            R″ represents identical or different radicals selected from            the group of —H, -phenyl, -benzyl, —CH₂—CH(CH₃)Ph, the C₁₋₂₀            alkyl radicals, preferably —CH₃, —CH₂CH₃, —CH₂CH₂CH₃,            —CH(CH₃)₂, —CH₂CH₂CH₂H₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃,            —C(CH₃)₃, and A represents an anion preferably selected from            chloride, bromide, iodide or methosulfate.

In another preferred embodiment, a method as contemplated herein isexemplified by the application of an agent (a) to the keratinousmaterial, wherein the agent (a) comprises at least one amino-modifiedsilicone polymer (a3) of formula (S-VII),

wherein m and n are numbers whose sum (m+n) is between 1 and 2000,preferably between about 50 and 150, n preferably assuming values fromabout 0 to about 1999 and from about 49 to about 149, and m preferablyassuming values from about 1 to about 2000, from about 1 to about 10.

According to the INCI declaration, these silicones are calledtrimethylsilylamodimethicones.

In a further preferred embodiment, a method as contemplated herein isexemplified by the application of an agent (a) to the keratinousmaterial, said agent (a) comprising at least one amino-modified siliconepolymer (a3) of formula (S-VIII)

in which R represents —OH, —O—CH₃ or a —CH₃ group and m, n1 and n2 arenumbers whose sum (m+n1+n2) is between about 1 and 2000, preferablybetween about 50 and 150, the sum (n1+n2) preferably assuming valuesfrom about 0 to about 1999 and from about 49 to about 149 and mpreferably assuming values from about 1 to about 2000, from about 1 toabout 10.

According to the INCI declaration, these amino-modified oramino-functionalized silicone polymers are known as amodimethicones.

Regardless of which amino-modified silicones are used, agents (a) ascontemplated herein are preferred which contain an amino-modifiedsilicone polymer whose amine number is above 0.25 meq/g, preferablyabove 0.3 meq/g and above 0.4 meq/g. The amine number represents themilliequivalents of amine per gram of the amino-functional silicone. Theamine number represents the milliequivalents of amine per gram of theamino-functional silicone.

In another preferred embodiment, a method as contemplated herein isexemplified by the application of an agent (a) to the keratinousmaterial, wherein the agent (a) comprises at least one amino-modifiedsilicone polymer (a3) of the formula of formula (S-IX),

where

-   -   m and n mean numbers chosen so that the sum (n+m) is in the        range 1 to 1000,    -   n is a number in the range 0 to 999 and m is a number in the        range 1 to 1000,    -   R1, R2 and R3, which are the same or different, denote a hydroxy        group or a C1-4 alkoxy group,    -   wherein at least one of R1 to R3 represents a hydroxy group.

Other preferred methods as contemplated herein are exemplified by theapplication of an agent (a) to the keratinous material, said agent (a)comprising at least amino-functional silicone polymer of the formula offormula (S-X)

in which

-   -   p and q mean numbers chosen so that the sum (p+q) is in the        range 1 to 1000,    -   p is a number in the range 0 to 999 and q is a number in the        range 1 to 1000,    -   R1 and R2, which are different, denote a hydroxy group or a C1-4        alkoxy group, at least one of R1 to R2 denoting a hydroxy group.

The silicones of the formulas (S-IX) and (S-X) differ in the grouping atthe Si atom carrying the nitrogen-containing group: In formula (S-IX),R2 represents a hydroxy group or a C1-4 alkoxy group, while the residuein formula (S-X) is a methyl group. The individual Si groupings, whichare marked with the indices m and n or p and q, do not have to bepresent as blocks; rather, the individual units can also be present in astatistically distributed manner, i.e., in the formulas (S-IX) and(S-X), not every R1-Si(CH₃)₂ group is necessarily bound to an—[O—Si(CH₃)₂] grouping.

Processes as contemplated herein in which an agent (a) containing atleast one amino-modified silicone polymer (a3) of the formula of theformula (S-XI) is applied to the keratin fibers have also proved to beparticularly effective with respect to the desired effects.

located in theA represents a group —OH, —O—Si(CH₃)₃,—O—Si(CH₃)₂OH,—O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃,—Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,b, n, and c stand for integers between 0 and 1000,with the specifications

-   -   n>0and b+c>0    -   at least one of the conditions A=—OH or D=—H is fulfilled.

In the above formula (S-XI), the individual siloxane units arestatistically distributed with the indices b, c, and n, i.e., they donot necessarily have to be block copolymers.

Particularly good effects about the improvement of the rub fastnesscould be observed when in the processes as contemplated herein an agent(a) was applied to the keratin material, which contained a special4-morpholinomethyl-substituted silicone polymer (a3). This veryparticularly preferred amino-functionalized silicone polymer comprisesat least one structural unit of the formula (S-XIII)

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is exemplified in that the agentcomprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of the formula (S-XIII)

Particularly good effects in terms of improving rub fastness were alsoobserved when an agent (a) containing a special4-morpholinomethyl-substituted silicone polymer (a3) was applied to thekeratin material in the processes as contemplated herein. This veryparticularly preferred amino-functionalized silicone polymer comprisesstructural units of the formulae (S-XII) and of the formula (S-XIII)

In an explicitly quite particularly preferred embodiment, a process ascontemplated herein is exemplified in that the agent (a) contains atleast one amino-modified silicone polymer (a3) which comprisesstructural units of the formula (S-XII) and of the formula (S-XIII)

Corresponding 4-morpholinomethyl-substituted silicone polymers aredescribed below.

A very particularly preferred amino-functionalized silicone polymer isknown by the name of Amodimethicone/Morpholinomethyl SilsesquioxaneCopolymer is known and commercially available from Wacker in the form ofthe raw material Belsil ADM 8301 E.

As a 4-morpholinomethyl-substituted silicone, for example, a siliconecan be used which has structural units of the formulae (S-XII),(S-XIII′) and (S-XIV′)

in whichR1 is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R2 is —CH₃, —OH, or —OCH₃.

Particularly preferred compositions (a) as contemplated herein containat least one 4-morpholinomethyl-substituted silicone of the formula(S-XV)

located in theR1 is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R2 is —CH₃, —OH, or —OCH₃.B represents a group —OH, —O—Si(CH₃)₃,—O—Si(CH₃)₂OH,—O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,a, b, and c stand independently for integers between 0 and 1000, withthe condition a+b+c>0m and n independently of each other stand for integers between 1 and1000

with the proviso that

-   -   at least one of the conditions B=—OH or D=—H is fulfilled,    -   the units a, b, c, m, and n are distributed statistically or        blockwise in the molecule.

Structural formula (Si-VI) is intended to illustrate that the siloxanegroups n and m do not necessarily have to be directly bonded to aterminal grouping B or D, respectively. Rather, in preferred formulas(Si-VI) a>0 or b>0 and in particularly preferred formulas (Si-VI) a>0and c>0, i.e., the terminal grouping B or D is preferably attached to adimethylsiloxy grouping. Also, in formula (Si-VI), the siloxane units a,b, c, m, and n are preferably statistically distributed.

The silicones used as contemplated herein represented by formula (Si-VI)can be trimethylsilyl-terminated (D or B=—Si(CH3)3), but they can alsobe dimethylsilylhydroxy-terminated on two sides ordimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated onone side. Silicones particularly preferred in the context of the presentdisclosure are selected from silicones in which.

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₃B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OHB=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OCH₃B=—O—Si(CH₃)₃ and D=—Si(CH₃)₂OHB=—O—Si(CH₃)₂OCH₃ and D=—Si(CH₃)₂OHto everyone.

To produce particularly resistant films, the agent (a) contains thesilicone polymer(s), in the alkoxy-modified and/or the amino-modifiedsilicone polymers, preferably in specific ranges of amounts.

Particularly flexible films of low tack were obtained when an agent (a)was used in the process as contemplated herein which contains—based onthe total weight of the agent (a)—one or more silicone polymers (a3) ina total amount of from about 0.1 to about 8.0% by weight, preferablyfrom about 0.1 to about 5.0% by weight, more preferably from about 0.1to about 3.0% by weight and very preferably from about 0.1 to about 0.5%by weight.

In the context of a further preferred embodiment, a process ascontemplated herein is exemplified in that the agent (a) contains—basedon the total weight of the agent (a)—one or more silicone polymers in atotal amount of from about 0.1 to about 15.0% by weight, preferably fromabout 0.5 to about 12.0% by weight, more preferably from about 1.0 toabout 10.0% by weight and very particularly preferably from about 2.0 toabout 8.0% by weight.

In an explicitly quite particularly preferred embodiment, a process ascontemplated herein is exemplified in that the agent (a) contains—basedon the total weight of the agent (a)—one or more alkoxy-modifiedsilicone polymers in a total amount of from about 0.1 to about 15.0% byweight, preferably from about 0.5 to about 12.0% by weight, morepreferably from about 1.0 to about 10.0% by weight and very particularlypreferably from about 2.0 to about 8.0% by weight.

In an explicitly quite particularly preferred embodiment, a process ascontemplated herein is exemplified in that the agent (a) contains—basedon the total weight of the agent (a)—one or more amino-modified siliconepolymers in a total amount of from about 0.1 to about 15.0% by weight,preferably from about 0.5 to about 12.0% by weight, more preferably fromabout 1.0 to about 10.0% by weight and very particularly preferably fromabout 2.0 to about 8.0% by weight.

pH Value of the Agent (a)

It has been found preferable if the agent (a) is made up in the form ofa water-containing agent adjusted to an alkaline pH.

To adjust the pH value, the agent (a) may contain at least onealkalizing agent.

To adjust the desired pH, the agents (a) may therefore also contain atleast one alkalizing agent. The pH values for the purposes of thepresent disclosure are pH values measured at a temperature of 22° C.

As alkalizing agent, agent (a) may contain, for example, ammonia,alkanolamines and/or basic amino acids.

The alkanolamines which can be used in the composition of the presentdisclosure are preferably selected from primary amines having a C₂-C₆alkyl base which carries at least one hydroxyl group. Preferredalkanolamines are selected from the group formed by 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol.

Alkanolamines particularly preferred as contemplated herein are selectedfrom 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol. Aparticularly preferred embodiment is therefore exemplified in that theagent as contemplated herein contains an alkanolamine selected from2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol as alkalizingagent.

A particularly preferred embodiment is therefore exemplified in that theagent as contemplated herein contains an alkanolamine selected from2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol as alkalizingagent. Preferred amino acids are amino carboxylic acids, especiallyα-(alpha)-amino carboxylic acids and ω-amino carboxylic acids, wherebyα-amino carboxylic acids are particularly preferred.

As contemplated herein, basic amino acids are those amino acids whichhave an isoelectric point pI of greater than 7.0.

Basic α-amino carboxylic acids contain at least one asymmetric carbonatom. In the context of the present invention, both possible enantiomerscan be used equally as specific compounds or their mixtures, especiallyas racemates. However, it is particularly advantageous to use thenaturally preferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine, and histidine, especially preferablyarginine and lysine. In another particularly preferred embodiment, anagent as contemplated herein is therefore exemplified in that thealkalizing agent is a basic amino acid from the group arginine, lysine,ornithine and/or histidine.

In addition, the product may contain other alkalizing agents, especiallyinorganic alkalizing agents. Inorganic alkalizing agents usable ascontemplated herein are preferably selected from the group formed bysodium hydroxide, potassium hydroxide, calcium hydroxide, bariumhydroxide, sodium phosphate, potassium phosphate, sodium silicate,sodium metasilicate, potassium silicate, sodium carbonate and potassiumcarbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan- 1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine,lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide,calcium hydroxide, barium hydroxide, sodium phosphate, potassiumphosphate, sodium silicate, sodium metasilicate, potassium silicate,sodium carbonate and potassium carbonate.

Although the agents (a) as contemplated herein are preferably adjustedto pH values in the alkaline range, it may nevertheless be necessary inprinciple to also use acidifiers in small amounts for fine adjustment ofthe desired pH value. Acidifiers suitable as contemplated herein are,for example, citric acid, lactic acid, acetic acid or also dilutemineral acids (such as hydrochloric acid, sulfuric acid, phosphoricacid).

However, in the course of the work leading to the present invention, ithas been found that the presence of the alkalizing agent or theadjustment of the alkaline pH is essential for the formation ofresistant films on the keratin material. The presence of excessiveamounts of acids can have a negative effect on the strength of thefilms. For this reason, it has proved preferable to keep the quantitiesof acids used in the medium (a) as low as possible. For this reason, itis advantageous if the total amount of organic and/or inorganic acidscontained in the agent (a) does not exceed a certain value.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the total amount of organic acids from the group ofcitric acid, tartaric acid, malic acid, and lactic acid contained in theagent (a) is below 1.0% by weight, preferably below 0.7% by weight, morepreferably below 0.5% by weight, even more preferably below 0.1% byweight and very particularly preferably below 0.01% by weight.In a further preferred embodiment, a process as contemplated herein isexemplified in that the total amount of inorganic acids from the groupof hydrochloric acid, sulfuric acid and phosphoric acid contained in theagent (a) is below 1.0% by weight, preferably below 0.7% by weight, morepreferably below 0.5% by weight, still more preferably below 0.1% byweight and very particularly preferably below 0.01% by weight.

The maximum total amounts of the acids contained in the agent (a) givenabove are always based on the total weight of the agent (a).

Agent (b)

The method of treating keratin material as contemplated hereincomprises, in addition to the application of agent (a), the applicationof agent (b). The agent (b) is exemplified in that it comprises at leastone film-forming polymer (b1).

Polymers are macromolecules with a molecular weight of at least 1000g/mol, preferably of at least 2500 g/mol, particularly preferably of atleast 5000 g/mol, which include identical, repeating organic units. Thepolymers of the present disclosure may be synthetically producedpolymers which are manufactured by polymerization of one type of monomeror by polymerization of different types of monomer which arestructurally different from each other. If the polymer is produced bypolymerizing a type of monomer, it is called a homo-polymer. Ifstructurally different monomer types are used in polymerization, theresulting polymer is called a copolymer.

The maximum molecular weight of the polymer depends on the degree ofpolymerization (number of polymerized monomers) and the batch size andis determined by the polymerization method. For the purposes of thepresent invention, it is preferred that the maximum molecular weight ofthe film-forming hydrophobic polymer (c) is not more than 10⁷ g/mol,preferably not more than 10⁶ g/mol and particularly preferably not morethan 10⁵ g/mol.

As contemplated herein, a film-forming polymer is a polymer which canform a film on a substrate, for example on a keratinic material or akeratinic fiber. The formation of a film can be demonstrated, forexample, by looking at the keratin material treated with the polymerunder a microscope.

The film-forming polymers (b1) in the agent (b) can be hydrophilic orhydrophobic.

In a first embodiment, it may be preferred to use at least onehydrophobic film-forming polymer in agent (b).

A hydrophobic polymer is a polymer that has a solubility in water at 25°C. (760 mmHg) of less than 1% by weight.

The water solubility of the film-forming, hydrophobic polymer can bedetermined in the following way, for example. 1.0 g of the polymer isplaced in a beaker. Make up to 100 g with water. A stir-fish is added,and the mixture is heated to 25° C. on a magnetic stirrer whilestirring. It is stirred for 60 minutes. The aqueous mixture is thenvisually assessed. If the polymer-water mixture cannot be assessedvisually due to a high turbidity of the mixture, the mixture isfiltered. If a proportion of undissolved polymer remains on the filterpaper, the solubility of the polymer is less than 1% by weight.

These include acrylic acid-type polymers, polyurethanes, polyesters,polyamides, polyurea's, cellulose polymers, nitrocellulose polymers,silicone polymers, acrylamide-type polymers, and polyisoprenes.

Particularly well suited film-forming, hydrophobic polymers are, forexample, polymers from the group of copolymers of acrylic acid,copolymers of methacrylic acid, homopolymers or copolymers of acrylicacid esters, homopolymers or copolymers of methacrylic acid esters,homopolymers or copolymers of acrylic acid amides, homopolymers orcopolymers of methacrylic acid amides, copolymers of vinylpyrrolidone,copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymersor copolymers of ethylene, homopolymers or copolymers of propylene,homopolymers or copolymers of styrene, polyurethanes, polyesters and/orpolyamides.

In a further preferred embodiment, an agent as contemplated herein isexemplified in that it contains at least one film-forming hydrophobicpolymer (c) selected from the group of copolymers of acrylic acid,copolymers of methacrylic acid, homopolymers or copolymers of acrylicacid esters, homopolymers or copolymers of methacrylic acid esters,homopolymers or copolymers of acrylic acid amides, homopolymers orcopolymers of methacrylic acid amides, copolymers of vinylpyrrolidone,copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymersor copolymers of ethylene, homopolymers or copolymers of propylene,homopolymers or copolymers of styrene, polyurethanes, polyesters and/orpolyamides.

The film-forming hydrophobic polymers, which are selected from the groupof synthetic polymers, polymers obtainable by radical polymerization ornatural polymers, have proved to be particularly suitable for solvingthe problem as contemplated herein.

Other particularly well-suited film-forming hydrophobic polymers can beselected from the homopolymers or copolymers of olefins, such ascycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinylamides, the esters, or amides of (meth)acrylic acid having at least oneC₁-C₂₀ alkyl group, an aryl group or a C₂-C₁₀ hydroxyalkyl group.

Other film-forming hydrophobic polymers may be selected from the homo-or copolymers of isooctyl (meth)acrylate; isonononyl (meth)acrylate;2-ethylhexyl (meth)acrylate; lauryl (meth)acrylate; isopentyl(meth)acrylate; n-butyl (meth)acrylate); isobutyl (meth)acrylate; ethyl(meth)acrylate; methyl (meth)acrylate; tert-butyl (meth)acrylate;stearyl (meth)acrylate; hydroxyethyl (meth)acrylate; 2-hydroxypropyl(meth)acrylate; 3-hydroxypropyl (meth)acrylate and/or mixtures thereof.

Other film-forming hydrophobic polymers may be selected from the homo-or copolymers of (meth)acrylamide; N-alkyl-(meth)acrylamides, in thosewith C2-C18 alkyl groups, such as N-ethyl-acrylamide,N-tert-butyl-acrylamide, le N-octyl-crylamide;N-di(C1-C4)alkyl-(meth)acrylamide.

Other preferred anionic copolymers are, for example, copolymers ofacrylic acid, methacrylic acid or their C₁-C₆ alkyl esters, as they aremarketed under the INCI Declaration Acrylates Copolymers. A suitablecommercial product is for example Aculyn® 33 from Rohm & Haas.Copolymers of acrylic acid, methacrylic acid or their C₁-C₆ alkyl estersand the esters of an ethylenically unsaturated acid and an alkoxylatedfatty alcohol are also preferred. Suitable ethylenically unsaturatedacids are especially acrylic acid, methacrylic acid and itaconic acid;suitable alkoxylated fatty alcohols are especially steareth-20 orceteth-20.

Very particularly preferred polymers on the market are, for example,Aculyn® 22 (Acrylates/Steareth-20 Me-thacrylate Copolymer), Aculyn® 28(Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 20010(Acryla-tes/Steareth-20 Itaconate Copolymer), Structure 30010(Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus®(Acrylates/Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer),Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C10-30 AlkylAcrylate Crosspolymer), Synthalen W 2000® (Acrylates/Palmeth-25 AcrylateCopolymer) or the Rohme and Haas distributed Soltex OPT(Acrylates/C12-22 Alkyl methacrylate Copolymer).

The homo- and copolymers of N-vinylpyrrolidone, vinylcaprolactam,vinyl-(C1-C₆)alkyl-pyrrole, vinyl-oxazole, vinyl-thiazole,vinylpyrimidine, vinylimidazole can be named as suitable polymers basedon vinyl monomers.

Furthermore, the copolymersoctylacrylamide/acrylates/butylaminoethyl-methacrylate copolymer, ascommercially marketed under the trade names AMPHOMER® or LOVOCRYL® 47 byNATIONAL STARCH, or the copolymers of acrylates/octylacrylamidesmarketed under the trade names DERMACRYL® LT and DERMACRYL® 79 byNATIONAL STARCH are particularly suitable.

Suitable olefin-based polymers include homopolymers and copolymers ofethylene, propylene, butene, isoprene and butadiene.

In another embodiment, the film-forming hydrophobic polymers may be theblock copolymers comprising at least one block of styrene or thederivatives of styrene. These block copolymers can be copolymers thatcontain one or more other blocks in addition to a styrene block, such asstyrene/ethylene, styrene/ethylene/butylene, styrene/butylene,styrene/isoprene, styrene/butadiene. Such polymers are commerciallydistributed by BASF under the trade name “Luvitol HSB”.

Surprisingly, it was found that particularly intense and washfastcolorations could be obtained when agent (b) contained at least onefilm-forming polymer (b1) selected from the group of acrylic acidhomopolymers and copolymers, methacrylic acid homopolymers andcopolymers, acrylic acid ester homopolymers and copolymers, methacrylicacid ester homopolymers and copolymers, homopolymers and copolymers ofacrylic acid amides, homopolymers and copolymers of methacrylic acidamides, homopolymers and copolymers of vinylpyrrolidone, homopolymersand copolymers of vinyl alcohol, homopolymers and copolymers of vinylacetate, homopolymers and copolymers of ethylene, homopolymers andcopolymers of propylene, homopolymers and copolymers of styrene,polyurethanes, polyesters and polyamides.In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (b) comprises at least one film-formingpolymer (b1) which is selected from the group of the homopolymers andcopolymers of acrylic acid, the homopolymers and copolymers ofmethacrylic acid, the homopolymers and copolymers of acrylic acidesters, the homopolymers and copolymers of methacrylic acid estershomopolymers and copolymers of acrylic acid amides, homopolymers andcopolymers of methacrylic acid amides, homopolymers and copolymers ofvinylpyrrolidone, homopolymers and copolymers of vinyl alcohol,homopolymers and copolymers of vinyl acetate, homopolymers andcopolymers of ethylene, homopolymers and copolymers of propylene,homopolymers and copolymers of styrene, polyurethanes, polyesters andpolyamides.

In a further embodiment, it may be preferred to use at least onehydrophilic film-forming polymer (b1) in the agent (b).

A hydrophilic polymer is a polymer that has a solubility in water at 25°C. (760 mmHg) of more than 1% by weight, preferably more than 2% byweight.

The water solubility of the film-forming, hydrophilic polymer can bedetermined in the following way, for example. 1.0 g of the polymer isplaced in a beaker. Make up to 100 g with water. A stir-fish is added,and the mixture is heated to 25° C. on a magnetic stirrer whilestirring. It is stirred for 60 minutes. The aqueous mixture is thenvisually assessed. A completely dissolved polymer appearsmarkoscopically homogeneous. If the polymer-water mixture cannot beassessed visually due to a high turbidity of the mixture, the mixture isfiltered. If no undissolved polymer remains on the filter paper, thesolubility of the polymer is more than 1% by weight.

Nonionic, anionic, and cationic polymers can be used as film-forming,hydrophilic polymers.

Suitable film-forming hydrophilic polymers can be selected, for example,from the group of polyvinylpyrrolidone (co)polymers, polyvinyl alcohol(co)polymers, vinyl acetate (co)polymers, carboxyvinyl (co)polymers,acrylic acid (co)polymers, methacrylic acid (co)polymers, natural gums,polysaccharides and/or acrylamide (co)polymers.

Furthermore, it is particularly preferred to use polyvinylpyrrolidone(PVP) and/or a vinylpyrrolidone-containing copolymer as film-forminghydrophilic polymer.

In another particularly preferred embodiment, an agent as contemplatedherein is exemplified in that it contains (c) at least one film-forming,hydrophilic polymer selected from the group of polyvinylpyrrolidone(PVP) and the copolymers of polyvinylpyrrolidone.

It is further preferred if the agent as contemplated herein containspolyvinylpyrrolidone (PVP) as the film-forming hydrophilic polymer.Surprisingly, the wash fastness of the dyeing's obtained with agentscontaining PVP (b9 was also particularly good.

Particularly well-suited polyvinylpyrrolidones are available, forexample, under the name Luviskol® K from BASF SE, especially Luviskol® K90 or Luviskol® K 85 from BASF SE.

The polymer PVP K30, which is marketed by Ashland (ISP, POI Chemical),can also be used as another explicitly very well suitedpolyvinylpyrrolidone (PVP). PVP K 30 is a polyvinylpyrrolidone which ishighly soluble in cold water and has the CAS number 9003-39-8. Themolecular weight of PVP K 30 is about 40000 g/mol.

Other particularly suitable polyvinylpyrrolidones are the substancesknown under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60,LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and availablefrom BASF.

The use of film-forming hydrophilic polymers (b1) from the group ofcopolymers of polyvinylpyrrolidone has also led to particularly good andwashfast color results.

Vinylpyrrolidone-vinyl ester copolymers, such as those marketed underthe trademark Luviskol® (BASF), are particularly suitable film-forminghydrophilic polymers. Luviskol VA 64 and Luviskol VA 73, bothvinylpyrrolidone/vinyl acetate copolymers, are particularly preferrednon-ionic polymers.

Of the vinylpyrrolidone-containing copolymers, a styrene/VP copolymerand/or a vinylpyrrolidone-vinyl acetate copolymer and/or a VP/DMAPAacrylates copolymer and/or a VP/vinyl caprolactam/DMAPA acrylatescopolymer are particularly preferred in cosmetic compositions.

Vinylpyrrolidone-vinyl acetate copolymers are marketed under the nameLuviskol® VA by BASF SE. For example, a VP/Vinyl Caprolactam/DMAPAAcrylates copolymer is sold under the trade name Aquaflex® SF-40 byAshland Inc. For example, a VP/DMAPA acrylates copolymer is marketed byAshland under the name Styleze CC-10 and is a highly preferredvinylpyrrolidone-containing copolymer.

Other suitable copolymers of polyvinylpyrrolidone may also be thoseobtained by reacting N-vinylpyrrolidone with at least one furthermonomer from the group of V-vinylformamide, vinyl acetate, ethylene,propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and/or vinylalcohol.

In another very particularly preferred embodiment, an agent ascontemplated herein is exemplified in that it comprises at least onefilm-forming, hydrophilic polymer (b1) selected from the group ofpolyvinylpyrrolidone (PVP), vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylenecopolymers, vinylpyrrolidone/propylene copolymers,vinylpyrrolidone/vinylcaprolactam copolymers,vinylpyrrolidone/vinylformamide copolymers and/or vinylpyrrolidone/vinylalcohol copolymers.

Another fussy copolymer of vinylpyrrolidone is the polymer known underthe INCI designation maltodextrin/VP copolymer.

Furthermore, intensively dyed keratin material, especially hair, withparticularly good wash fastness could be obtained if a non-ionic,film-forming, hydrophilic polymer was used as the film-forming,hydrophilic polymer.

In another embodiment, the agent (b) may contain at least one nonionic,film-forming, hydrophilic polymer (b1).

As contemplated herein, a non-ionic polymer is understood to be apolymer which in a protic solvent—such as water—under standardconditions does not carry structural units with permanent cationic oranionic groups, which must be compensated by counterions whilemaintaining electron neutrality. Cationic groups include quaternizedammonium groups but not protonated amines Anionic groups includecarboxylic and sulphonic acid groups.

Preference is given to products containing, as a non-ionic,film-forming, hydrophilic polymer, at least one polymer selected fromthe group of

-   -   Polyvinylpyrrolidone,    -   Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic        acids having 2 to 18 carbon atoms, of N-vinylpyrrolidone and        vinyl acetate,    -   Copolymers of N-vinylpyrrolidone and N-vinylimidazole and        methacrylamide,    -   Copolymers of N-vinylpyrrolidone and N-vinylimidazole and        acrylamide,    -   Copolymers of N-vinylpyrrolidone with N,N-di(C1 to        C4)-alkylamino-(C2 to C4)-alkylacrylamide,

If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it isagain preferable if the molar ratio of the structural units contained inthe monomer N-vinylpyrrolidone to the structural units of the polymercontained in the monomer vinyl acetate is in the range from about 20:80to about 80:20, in particular from about 30:70 to about 60:40. Suitablecopolymers of vinyl pyrrolidone and vinyl acetate are available, forexample, under the trademarks Luviskol® VA 37, Luviskol® VA 55,Luviskol® VA 64 and Luviskol® VA 73 from BASF SE.

Another particularly preferred polymer is selected from the INCIdesignation VP/Methacrylamide/Vinyl Imidazole Copolymer, which isavailable under the trade name Luviset Clear from BASF SE.

Another particularly preferred non-ionic, film-forming, hydrophilicpolymer is a copolymer of N-vinylpyrrolidone andN,N-dimethylaminiopropylmethacrylamide, which is sold under the INCIdesignation VP/DMAPA Acrylates Copolymer e.g., under the trade nameStyleze® CC 10 by ISP.

A cationic polymer of interest is the copolymer of N-vinylpyrrolidone,N-vinylcaprolactam, N-(3-dimethylaminopropyl)methacrylamide and3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCIdesignation): Polyquaternium-69), which is marketed, for example, underthe trade name AquaStyle® 300 (28-32% by weight active substance inethanol-water mixture, molecular weight 350000) by ISP.

Other suitable film-forming, hydrophilic polymers include.

-   -   Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as        offered under the designations Luviquat® FC 370, FC 550 and the        INCI designation Polyquaternium-16 as well as FC 905 and HM 552,    -   Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, as they        are commercially available with acrylic acid esters and acrylic        acid amides as a third monomer component, for example under the        name Aquaflex® SF 40.

Polyquaternium-11 is the reaction product of diethyl sulphate with acopolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate.Suitable commercial products are available under the names Dehyquart® CC11 and Luviquat® PQ 11 PN from BASF SE or Gafquat 440, Gafquat 734,Gafquat 755 or Gafquat 755N from Ashland Inc.

Polyquaternium-46 is the reaction product of vinylcaprolactam andvinylpyrrolidone with methylvinylimidazolium methosulfate and isavailable for example under the name Luviquat® Hold from BASF SE.Polyquaternium-46 is preferably used in an amount of 1 to 5% byweight—based on the total weight of the cosmetic composition. Itparticularly prefers to use polyquaternium-46 in combination with acationic guar compound. It is even highly preferred thatpolyquaternium-46 is used in combination with a cationic guar compoundand polyquaternium-11.

Suitable anionic film-forming, hydrophilic polymers can be, for example,acrylic acid polymers, which can be in non-crosslinked or crosslinkedform. Such products are sold commercially under the trade names Carbopol980, 981, 954, 2984 and 5984 by Lubrizol or under the names Synthalen Mand Synthalen K by 3V Sigma (The Sun Chemicals, Inter Harz).

Examples of suitable film-forming, hydrophilic polymers from the groupof natural gums are xanthan gum, gellan gum, carob gum.

Examples of suitable film-forming hydrophilic polymers from the group ofpolysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose,ethyl cellulose and carboxymethyl cellulose.

Suitable film-forming, hydrophilic polymers from the group of acrylamdesare, for example, polymers which are produced from monomers of(methy)acrylamido-C₁-C₄-alkyl sulphonic acid or the salts thereof.Corresponding polymers may be selected from the polymers ofpolyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid,polyacrylamidopropanesulfonic acid,poly2-acrylamido-2-methylpropanesulfonic acid,poly-2-methylacrylamido-2-methylpropanesulfonic acid and/orpoly-2-methylacrylamido-n-butanesulfonic acid.

Preferred polymers of the poly(meth)arylamido-C1-C4-alkyl sulphonicacids are cross-linked and at least 90% neutralized. These polymers canor cannot be cross-linked.

Cross-linked and fully or partially neutralized polymers of thepoly-2-acrylamido-2-methylpropane sulfonic acid type are available underthe INCI designation “AmmoniumPolyacrylamido-2-methyl-propanesulphonates” or “AmmoniumPolyacryldimethyltauramides”.

Another preferred polymer of this type is the cross-linkedpoly-2-acrylamido-2-methyl-propanesulphonic acid polymer marketed byClamant under the trade name Hostacerin AMPS, which is partiallyneutralized with ammonia.

In a further explicitly quite particularly preferred embodiment, aprocess as contemplated herein is exemplified in that the agent (b)comprises at least one anionic, film-forming, polymer (b1).

In this context, the best results were obtained when the agent (b)contains at least one film-forming polymer (b1) comprising at least onestructural unit of formula (P-I) and at least one structural unit offormula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (b) comprises at least one film-formingpolymer (b1) which comprises at least one structural unit of the formula(P-I) and at least one structural unit of the formula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.

When M represents a hydrogen atom, the structural unit of the formula(P-I) is based on an acrylic acid unit.

When M stands for an ammonium counterion, the structural unit of theformula (P-I) is based on the ammonium salt of acrylic acid.When M stands for a sodium counterion, the structural unit of theformula (P-I) is based on the sodium salt of acrylic acid.When M stands for a potassium counterion, the structural unit of theformula (P-I) is based on the potassium salt of acrylic acid.If M stands for a half equivalent of a magnesium counterion, thestructural unit of the formula (P-I) is based on the magnesium salt ofacrylic acid.If M stands for a half equivalent of a calcium counterion, thestructural unit of the formula (P-I) is based on the calcium salt ofacrylic acid.

The film-forming polymer or polymers (b1) as contemplated herein arepreferably used in certain ranges of amounts in the agent (b) ascontemplated herein. In this context, it has proved particularlypreferable for solving the problem as contemplated herein if the agent(b) contains—based on the total weight of the agent (b)—one or morefilm-forming polymers (b1) in a total amount of from about 0.1 to about18.0% by weight, preferably from about 1.0 to about 16.0% by weight,more preferably from about 5.0 to about 14.5% by weight and veryparticularly preferably from about 8.0 to about 12.0% by weight.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the agent (b) contains—based on the total weight ofthe agent (b)—one or more film-forming polymers (b1) in a total amountof from about 0.1 to about 18.0% by weight, preferably from about 1.0 toabout 16.0% by weight, more preferably from about 5.0 to about 14.5% byweight and very particularly preferably from about 8.0 to about 12.0% byweight.

The application of agent (b) is intended to seal and fix the filminitially produced by the application of agent (a). Here, the filmproduced by agent (b) is preferably not colored itself. In this way, theuncolored film produced by agent (b) is above the colored film producedby agent (a) and can protect the latter from external influences. Inthis way, it can also be ensured that any abrasion of the second film(b) that takes place to a certain extent does not lead to any colorchanges in the entire film system. It is therefore particularlypreferred if the agent (b) contains no or only exceedingly small amountsof colorant compounds.

In a further preferred embodiment, a process as contemplated herein isexemplified in that the total amount of colorant compounds from thegroup of pigments and direct dyes contained in the agent (b) is below0.2% by weight, preferably below 0.1% by weight, even more preferablybelow 0.05% by weight and very particularly preferably below 0.01% byweight.

The total amount of colorant compounds from the group of pigments anddirect dyes is based on the total weight of the formulation (b).

Other Ingredients

The agents (a) and (b) used in the process described above may furthercontain one or more additional optional ingredients.

The products may also contain one or more surfactants. The termsurfactants refer to surface-active substances. A distinction is madebetween anionic surfactants of a hydrophobic residue and a negativelycharged hydrophilic head group, amphoteric surfactants, which carry botha negative and a compensating positive charge, cationic surfactants,which in addition to a hydrophobic residue have a positively chargedhydrophilic group, and non-ionic surfactants, which have no charges butstrong dipole moments and are strongly hydrated in aqueous solution.

Zwitterionic surfactants are those surface-active compounds which carryat least one quaternary ammonium group and at least one —COO⁽⁻⁾- or —SO₃⁽⁻⁾ group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines such as theN-alkyl-N,N-dimethylammonium-glycinate, for example thecocoalkyl-dimethylammoniumglycinate,N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example,cocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is thefatty acid amide derivative known under the INCI name cocamidopropylbetaine.

Ampholytic surfactants are surface-active compounds which, apart from aC₈-C₂₄ alkyl or acyl group, contain at least one free amino group and atleast one —COOH— or —SO₃H group in the molecule and can form internalsalts. Examples of suitable ampholytic surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids each with about 8 to 24 C atoms in the alkyl group. Typicalexamples of amphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, amino propionates, aminoglycinate,imidazoliniumbetaines and sulfobetaines.

Particularly preferred ampholytic surfactants areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈ acylsarcosine.

The products may also additionally contain at least one non-ionicsurfactant. Suitable non-ionic surfactants are alkyl polyglycosides aswell as alkylene oxide addition products to fatty alcohols and fattyacids with 2 to 30 mol ethylene oxide per mol fatty alcohol or fattyacid. Preparations with good properties are also obtained if theycontain as non-ionic surfactants fatty acid esters of ethoxylatedglycerol reacted with at least 2 mol ethylene oxide. The non-ionicsurfactants are used in a total quantity of about 0.1 to about 45% byweight, preferably about 1 to about 30% by weight and very preferablyabout 1 to about 15% by weight—based on the total weight of therespective agent.

In addition, the products may also contain at least one cationicsurfactant. Cationic surfactants are surfactants, i.e., surface-activecompounds, each with one or more positive charges. Cationic surfactantscontain only positive charges. Usually, these surfactants are composedof a hydrophobic part and a hydrophilic head group, the hydrophobic partusually of a hydrocarbon backbone (e.g., of one or two linear orbranched alkyl chains) and the positive charge(s) being in thehydrophilic head group. Examples of cationic surfactants are:

-   -   quaternary ammonium compounds which, as hydrophobic radicals,        may carry one or two alkyl chains with a chain length of 8 to 28        C atoms,    -   quaternary phosphonium salts substituted with one or more alkyl        chains with a chain length of 8 to 28 C atoms or    -   tertiary sulfonium salts.

Furthermore, the cationic charge can also be part of a heterocyclic ring(e.g., an imidazolium ring or a pyridinium ring) in the form of an oniumstructure. In addition to the functional unit carrying the cationiccharge, the cationic surfactant may also contain other unchargedfunctional groups, as is the case for example with esterquats. Thecationic surfactants are used in a total quantity of about 0.1 to about45 wt. %, preferably about 1 to about 30 wt. % and most preferably about1 to about 15 wt. %—based on the total weight of the respective agent.

Furthermore, the compositions as contemplated herein may also contain atleast one anionic surfactant. Anionic surfactants are surface-activeagents with exclusively anionic charges (neutralized by a correspondingcounter cation). Examples of anionic surfactants are fatty acids, alkylsulphates, alkyl ether sulphates and ether carboxylic acids with 12 to20 C atoms in the alkyl group and up to 16 glycol ether groups in themolecule.

The anionic surfactants are used in a total quantity of about 0.1 toabout 45 wt. %, preferably about 1 to about 30 wt. % and most preferablyabout 1 to about 15 wt. %—based on the total weight of the respectiveagent.

They may also contain other active substances, auxiliaries andadditives, such as solvents, fatty components such as C₅-C₃₀ fattyalcohols, C₅-C₃₀ fatty acid triglycerides, C₈-C₃₀ fatty acidmonoglycerides, C₈-C₃₀ fatty acid diglycerides and/or hydrocarbons;structural agents such as glucose, maleic acid and lactic acid; hairconditioning compounds such as phospholipids, for example lecithin andcephalins; perfume oils, dimethylisosorbide and cyclodextrins; fiberstructure-improving active substances, in particular mono-, di- andoligosaccharides such as glucose, galactose, fructose, fructose andlactose; dyes for coloring the composition; anti-dandruff activesubstances such as Piroctone Olamine, Zinc Omadine and Climbazol; aminoacids and oligopeptides; protein hydrolysates on animal and/or vegetablebasis, as well as in the form of their fatty acid condensation productsor optionally anionic or cationically modified derivatives; vegetableoils; sunscreens and UV-blockers; active ingredients such as panthenol,pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acidsand their salts, and bisabolol; polyphenols, in particularhydroxycinnamic acids, 6,7-dihydroxycumarine, hydroxybenzoic acids,catechine, tannine, leukoanthocyanidine, anthocyanidine, flavanone,flavone and flavonols; ceramides or pseudoceramides; vitamins,provitamins and vitamin precursors; plant extracts; fats and waxes suchas fatty alcohols, beeswax, montan wax and paraffins; swelling andpenetrating substances such as glycerol, propylene glycol monoethylether, carbonates, hydrogen carbonates, guanidines, ureas and primary,secondary and tertiary phosphates; opacifiers such as latex, styrene/PVPand styrene/acrylamide copolymers; pearlescent agents such as ethyleneglycol mono- and distearate and PEG-3 distearate; and blowing agentssuch as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and air.

The selection of these other substances will be made by the specialistaccording to the desired properties of the agents. About other optionalcomponents and the quantities of these components used, explicitreference is made to the relevant manuals known to the specialist. Theadditional active ingredients and auxiliary substances are preferablyused in the preparations as contemplated herein in quantities of about0.0001 to about 25% by weight each, about 0.0005 to about 15% by weight,based on the total weight of the respective agent.

Process for Dyeing Keratin Materials

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous materials, to human hair. Thus, agents (a) and (b) arethe ready-to-use agents. The agents (a) and (b) are different.

In principle, agents (a) and (b) can be applied simultaneously orsuccessively, whereby successive application is preferred.

The best results were obtained when agent (a) was first applied to thekeratin materials in a first step and then agent (b) was applied in asubsequent step.

Quite particularly preferred, therefore, is a process for treatingkeratinous material, for coloring keratinous material, in particularhuman hair, comprising the following steps in the order indicated:

-   -   in a first step, applying an agent (a) to the keratinous        material, the agent comprising (a):        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   in a second step, applying an agent (b) to the keratinous        material, the agent comprising (b): (b1) at least one        film-forming polymer.

The agents (a) and (b) are particularly preferably applied within oneand the same dyeing process, which means that there is a period of amaximum of several hours between the application of agents (a) and (b).

In a further preferred embodiment, a method as contemplated herein isexemplified in that first the agent (a) is applied, and then the agent(b) is applied, the time between the application of the agents (a) and(b) being at most 24 hours, preferably at most 12 hours and particularlypreferably at most 6 hours.

A distinguishing feature of the agent (a) is its content of at least onereactive organic silicon compound (a1). The reactive organic siliconcompound(s) (a1) undergoes an oligomerization or polymerization reactionand thus functionalizes the hair surface as soon as it meets it. In thisway, a first, film is formed. The coloring compounds (a2) areincorporated into the film so that it is colored. In the second step ofthe process, a second, polymer-containing agent (b) is now applied tothe hair. During the application of agent (b), the film-forming polymersinteract with the silane film and are thus bound to the keratinmaterials. Here, the technical application properties of the resultingdyeing can be further improved by selecting the optimum processconditions.

In the context of a further form of execution, a procedure comprisingthe following steps in the order indicated is particularly preferred.

(1) Application of agent (a) on the keratinous material,(2) Allow the agent (a) to act for a period of 10 seconds to 10 minutes,preferably from about 10 seconds to about 5 minutes,(3) if necessary, rinse the keratinous material with water,(4) Application of agent (b) on the keratinous material,(5) Allow the agent (b) to act for a period of about 30 seconds to about30 minutes, preferably from about 30 seconds to about 10 minutes, and(6) Rinse the keratinous material with water.

The rinsing of the keratinous material with water in steps (3) and (6)of the process is understood, as contemplated herein, to mean that onlywater is used for the rinsing process, without any other agents otherthan agents (a) and (b).

In a first step (1), agent (a) is applied to the keratin materials,especially human hair.

After application, the agent (a) can act on the keratin materials. Inthis context, application times from about 10 seconds to about 10minutes, preferably from about 20 seconds to about 5 minutes andespecially preferably from about 30 seconds to about 2 minutes on thehair have proven to be particularly beneficial.

In a preferred embodiment of the method as contemplated herein, theagent (a) can now be rinsed from the keratin materials before the agent(b) is applied to the hair in the subsequent step.

Dyeing's with also good wash fastness were obtained when agent (b) wasapplied to the keratin materials which were still exposed to agent (a).

In step (4), agent (b) is now applied to the keratin materials. Afterapplication, let the agent (b) act on the hair.

The process as contemplated herein allows the production of dyeing'swith particularly good intensity and wash fastness even with a shortexposure time of agent (b). Application times from about 10 seconds toabout 10 minutes, preferably from about 20 seconds to about 5 minutesand most preferably from about 30 seconds to about 3 minutes on the hairhave proven to be particularly beneficial.

In step (6), agent (b) (and any remaining agent (a)) is rinsed out ofthe keratin material with water.

In the context of a further form of execution, a procedure comprisingthe following steps in the order indicated is particularly preferred.

(1) Application of agent (a) on the keratinous material,(2) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(3) if necessary, rinse the keratinous material with water,(4) Application of agent (b) on the keratinous material,(5) Allow the agent (b) to act for a period of about 30 seconds to about30 minutes, preferably from about 30 seconds to about 10 minutes, and(6) Rinse the keratinous material with water.

In this embodiment, the sequence of steps (1) to (6) preferably takesplace within 24 hours.

The agent (a) contains with the organic silicon compound(s) a class ofhighly reactive compounds which can undergo hydrolysis oroligomerization and/or polymerization when used. Due to their highreactivity, these organic silicon compounds form a film on the keratinmaterial.

To avoid premature oligomerization or polymerization, it is ofconsiderable advantage to the user to prepare the ready-to-use agent (a)only shortly before application.

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) preparing an agent (a) by mixing a first agent (a′) and a secondagent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms, and    -   the second agent (a″) comprises at least one colorant compound        (a2) selected from the group of pigments and/or direct dyes,        (2) Application of agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of about 10 seconds        to about 10 minutes, preferably from about 10 seconds to about 5        minutes,        (4) if necessary, rinse the keratinous material with water,        (4) Application of agent (b) on the keratinous material,        (5) Allowing the agent (b) to act for a period of about 30        seconds to about 30 minutes, preferably from about 30 seconds to        about 10 minutes,        (6) if necessary, rinse the keratinous material with water.

To be able to provide a formulation that is as stable as possible instorage, the agent (a′) itself is preferably formulated to be low inwater or water-free.

In a preferred embodiment, a multicomponent packaging unit(kit-of-parts) as contemplated herein is exemplified in that the agent(a′)—based on the total weight of the agent (a′)—contains a watercontent of from about 0.001 to about 10.0% by weight, preferably fromabout 0.5 to about 9.0% by weight, more preferably from about 1.0 toabout 8.0% by weight and very particularly preferably from about 1.5 toabout 7.0% by weight.

The agent (a″) contains water. In a preferred embodiment, amulticomponent packaging unit (kit-of-parts) as contemplated herein isexemplified in that the agent (a″)—based on the total weight of theagent (a2)—has a water content of from about 15 to about 100% by weight,preferably from about 35 to about 100% by weight, more preferably fromabout 55 to about 100% by weight, still more preferably from about 65 toabout 100% by weight and very particularly preferably from about 75 toabout 100% by weight.

Within this embodiment, the ready-to-use agent (a) is now prepared bymixing agents (a′) and (a″).

For example, the user may first stir or shake the agent (a′) containingthe organic silicon compound(s) (a1) with the aqueous dye-containingagent (a″). The user can now apply this mixture of (a′) and (a″) to thekeratin materials—either immediately after its preparation or after ashort reaction time of 10 seconds to 20 minutes. Afterwards, the usercan apply agent (b) as described above.

The optionally included silicone polymer (a3) can now be incorporatedinto the agent (a′) or into the agent (a″). Preferably, silicone polymer(a3) is incorporated into the agent (a″).

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) preparing an agent (a) by mixing a first agent (a′) and a secondagent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms and furthermore at least one silicone polymer        (a3), and    -   the second agent (a″) comprises at least one colorant compound        (a2) selected from the group of pigments and/or direct dyes,        (2) Application of agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of 10 seconds to 10        minutes, preferably from 10 seconds to 5 minutes,        (4) if necessary, rinse the keratinous material with water,        (4) Application of agent (b) on the keratinous material,        (5) Allowing the agent (b) to act for a period of 30 seconds to        30 minutes, preferably from 30 seconds to 10 minutes,        (6) if necessary, rinse the keratinous material with water.

In the context of a further embodiment, particularly preferred is amethod comprising the following steps in the order indicated.

(1) preparing an agent (a) by mixing a first agent (a′) and a secondagent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms, and    -   the second agent (a″) comprises at least one colorant compound        (a2) selected from the group of pigments and/or direct dyes and        furthermore at least one silicone polymer (a3),        (2) Application of agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of about 10 seconds        to about 10 minutes, preferably from about 10 seconds to about 5        minutes,        (4) if necessary, rinse the keratinous material with water,        (4) Application of agent (b) on the keratinous material,        (5) Allowing the agent (b) to act for a period of about 30        seconds to about 30 minutes, preferably from about 30 seconds to        about 10 minutes,        (6) if necessary, rinse the keratinous material with water.

In a further preferred embodiment, a process as contemplated herein canalso be exemplified in that the silicone polymer(s) (a3) is/are providedin a third separately prepared agent (a′″).

Preferred in the context of this further embodiment is a methodcomprising the following steps in the order indicated.

(1) preparing an agent (a) by mixing a first agent (a′) and a secondagent (a″) and a third agent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms, and    -   the second agent (a″) comprises at least one colorant compound        (a2) selected from the group of pigments and/or direct dyes, and    -   the third agent (a″) comprises at least one silicone polymer        (a3),        (2) Application of agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of about 10 seconds        to about 10 minutes, preferably from about 10 seconds to about 5        minutes,        (4) if necessary, rinse the keratinous material with water,        (4) Application of agent (b) on the keratinous material,        (5) Allowing the agent (b) to act for a period of about 30        seconds to about 30 minutes, preferably from about 30 seconds to        about 10 minutes,        (6) if necessary, rinse the keratinous material with water.

Multi-Component Packaging Unit (Kit-of-Parts)

To increase user comfort, the user is preferably provided with allrequired resources in the form of a multi-component packaging unit(kit-of-parts).

A second subject matter of the present disclosure is therefore amulti-component packaging unit (kit-of-parts) for coloring keratinicmaterial, comprehensively packaged separately from one another.

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):    -   (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and

a third container containing an agent (b), wherein the agent contains(b):

-   -   (b1) at least one film-forming polymer,        wherein the components (a1), (a2) and (b1) were disclosed in        detail in the description of the first subject matter of the        invention.

The organic silicon compounds (a1) from the group of silanes with one,two or three silicon atoms contained in agent (a) of the kit correspondto the organic silicon compounds that were also used in agent (a) of thepreviously described process.

The colorant compound (a2) from the group of pigments and/or direct dyescontained in the agent (a″) of the kit corresponds to the colorantcompounds also used in agent (a) of the previously described process.

The film-forming polymers (b1) contained in agent (b) of the kitcorrespond to the film-forming polymers that were also used in agent (b)of the previously described process.

In this context, it is again possible to use the optionally includedsilicone polymer (a3) To be made up in the agent (a′), in the agent (a″)or in a further agent (a′″).

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another.

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):    -   at least one organic silicon compound (a1) from the group of        silanes with one, two or three silicon atoms and furthermore at        least one silicone polymer (a3), and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   a third container containing an agent (b), wherein the agent        contains (b):    -   (b1) at least one film-forming polymer,        wherein the components (a1), (a2), (3) and (b1) were disclosed        in detail in the description of the first subject matter of the        invention.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another.

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):    -   at least one organic silicon compound (a1) from the group of        silanes with one, two or three silicon atoms and furthermore at        least one silicone polymer (a3), and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and

a third container containing an agent (am), wherein the agent (a′″) is awater-containing cosmetic carrier

a third container containing an agent (b), wherein the agent contains(b):

-   -   (b1) at least one film-forming polymer,        wherein the components (a1), (a2), (3) and (b1) were disclosed        in detail in the description of the first subject matter of the        invention.

In this embodiment, agents (a′) and (a″) have a low water content. Toprepare the ready-to-use agent (a), agents (a′), (a″) and (a′) aremixed. In this case, the agent (a″″) represents a water-containingcosmetic carrier.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another.

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):    -   at least one organic silicon compound (a1) from the group of        silanes having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and furthermore at least one        silicone polymer (a3), and

a third container containing an agent (b), wherein the agent contains(b):

-   -   (b1) at least one film-forming polymer,        wherein the components (a1), (a2), (a3) and (b1) were disclosed        in detail in the description of the first subject matter of the        invention.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another.

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):    -   at least one organic silicon compound (a1) from the group of        silanes having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):    -   (a2) at least one colorant compound selected from the group of        pigments and/or direct dyes, and    -   a third container comprising an agent (a′″), said agent        comprising (a′″):    -   at least one silicone polymer (a3), and

fourth container containing agent (b), wherein the agent contains (b):

-   -   (b1) at least one film-forming polymer,        wherein the components (a1), (a2), (a3) and (b1) were disclosed        in detail in the description of the first subject matter of the        invention.

With respect to the other preferred embodiments of the multi-componentpackaging unit as contemplated herein, the same applies mutatis mutandisto the procedure as contemplated herein.

EXAMPLES Example 1

The following formulations have been produced (unless otherwiseindicated, all figures are in % by weight)

Agent (a′) Agent (a′) in wt.. % (3-Aminopropyl)triethoxysilane (a1) 20.0Methyltrimethoxysilane (a1) 70.0 Water ad 100

Agent (a″) Agent (a″) in wt.. % Phthalocyanine blue pigment CI 74160(a3) 5.0 PEG-12 Dimethicone 5.0 Hydroxyethyl cellulose 1.0 Water ad 100

The ready-to-use agent (a) was prepared by mixing 5.0 g of agent (a′)and 20.0 g of agent (a″). The pH value of the agent (a) was adjusted toa value of 10.5 by adding ammonia or lactic acid. Then the agent (a)could stand for about 5 minutes.

Agent (b) Agent (b) in wt.. % Ethylene/Sodium Acrylate Copolymer (b1)40.0 25% solution Water ad 100

The agent (a) was massaged into one strand of hair at a time (Kerling,Euronatural hair white), and left to act for 1 minute. The agent (a) wasthen rinsed with water.

Subsequently, agent (b) was applied to the hair strand, left to act for1 minute and then also rinsed with water.

On the hair strand was obtained intense blue coloration with goodfastness to washing and particularly good fastness to rubbing.

Example 2

The following formulations have been produced (unless otherwiseindicated, all figures are in % by weight)

Agent (a′) Agent (a′) in wt.. % (3-Aminopropyl)triethoxysilane (a1) 20.0Methyltrimethoxysilane (a1) 70.0 Water ad 100

Agent (a″) Agent (a″) in wt.. % Pigment permanent red R CI 12085 60.01-[(2-chloro-4-nitrophenyl)azo]-2-naphthol (a3) PEG-12 Dimethicone 40.0

Agent (a″) (cosmetic carrier) Agent (a′′′) in wt.. % Hydroxyethylcellulose 1.0 Water ad 100

The ready-to-use agent (a) was prepared by mixing 5.0 g of agent (a′)and 5.0 g of agent (a″) and 20.0 g of agent (a″). The pH value of theagent (a) was adjusted to a value of 10.5 by adding ammonia or lacticacid. Then the agent (a) could stand for about 5 minutes.

Agent (b) Agent (b) in wt.. % Ethylene/Sodium Acrylate Copolymer (b1)40.0 25% solution Water ad 100

The agent (a) was massaged into one strand of hair at a time (Kerling,Euronatural hair white), and left to act for 1 minute. The agent (a) wasthen rinsed with water.

Subsequently, agent (b) was applied to the hair strand, left to act for1 minute and then also rinsed with water.

An intense red coloration with good wash fastness particularly good rubfastness was obtained.

Example 3

The following formulations have been produced (unless otherwiseindicated, all figures are in % by weight)

Agent (a′) Agent (a′) in wt.. % (3-Aminopropyl)triethoxysilane (a1) 20.0Methyltrimethoxysilane (a1) 70.0 Water ad 100

Agent (a″) Agent (a″) in wt.. % Pigment permanent red R CI 12085 100.01-[(2-chloro-4-nitrophenyl)azo]-2-naphthol (a3)

Agent (a′′′) Agent (a′′′) in wt.. % Hydroxyethyl cellulose 1.0 PEG-12Dimethicone 40.0 Water ad 100

The ready-to-use agent (a) was prepared by mixing 5.0 g of agent (a′)and 5.0 g of agent (a″) and 20.0 g of agent (a″). The pH value of theagent (a) was adjusted to a value of 10.5 by adding ammonia or lacticacid. Then the agent (a) could stand for about 5 minutes.

Agent (b) Agent (b) in wt.. % Ethylene/Sodium Acrylate Copolymer (b1)40.0 25% solution Water ad 100

The agent (a) was massaged into one strand of hair at a time (Kerling,Euronatural hair white), and left to act for 1 minute. The agent (a) wasthen rinsed with water.

Subsequently, agent (b) was applied to the hair strand, left to act for1 minute and then also rinsed with water.

An intense red coloration with good wash fastness particularly good rubfastness was obtained.

While at least one exemplary embodiment has been presented in theforegoing detailed description, it should be appreciated that a vastnumber of variations exist. It should also be appreciated that theexemplary embodiment or exemplary embodiments are only examples, and arenot intended to limit the scope, applicability, or configuration of thevarious embodiments in any way. Rather, the foregoing detaileddescription will provide those skilled in the art with a convenient roadmap for implementing an exemplary embodiment as contemplated herein. Itbeing understood that various changes may be made in the function andarrangement of elements described in an exemplary embodiment withoutdeparting from the scope of the various embodiments as set forth in theappended claims.

1. Process for dyeing keratinous material comprising the followingsteps: applying an agent (a) to the keratinous material, wherein theagent (a) comprises: (a1) at least one organic silicon compound selectedfrom the group of silanes having one, two or three silicon atoms, and(a2) at least one colorant compound selected from the group of pigmentsand/or direct dyes, and applying an agent (b) to the keratinousmaterial, wherein the agent (b) comprises: (b1) at least onefilm-forming polymer.
 2. Process according to claim 1, wherein the agent(a) comprises at least one organic silicon compound (a1) of the formula(I) and/or (II)R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ independently represent ahydrogen atom or a C₁-C₆ alkyl group, L is a linear or branched divalentC₁-C₂₀ alkylene group, R₃, R₄ independently of one another represent aC₁-C₆ alkyl group, a stands for an integer from about 1 to about 3, andb stands for the integer 3−a, and wherein in the organic siliconcompound of formula (II)(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II),R5, R5′, R5″, R6, R6′ and R6″ independently represent a C₁-C₆ alkylgroup, A, A′, A″, A′″ and A″″ independently represent a linear orbranched divalent C₁-C₂₀ alkylene group, R₇ and R₈ independentlyrepresent a hydrogen atom, a C₁-C₆ alkyl group, a hydroxy C₁-C₆ alkylgroup, a C₂-C₆ alkenyl group, an amino C₁-C₆ alkyl group or a group offormula (III)-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III), c, stands for an integer from 1to 3, d stands for the integer 3−c, c′ stands for an integer from 1 to3, d′ stands for the integer 3−c′, c″ stands for an integer from 1 to 3,d″ stands for the integer 3−c″, e stands for 0 or 1, f stands for 0 or1, g stands for 0 or 1, h stands for 0 or 1, provided that at least oneof e, f, g, and h is different from
 0. 3. The method according to claim1, wherein the agent (a) comprises at least one organic silicon compound(a1) of formula (I),R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ both represent a hydrogenatom, and L represents a linear, divalent C₁-C₆-alkylene group, R₃, R₄independently represent a methyl group or an ethyl group, and a standsfor the number 3 and b stands for the number
 0. 4. The agent accordingto claim 1, wherein the agent (a) comprises at least one organic siliconcompound (a1) of formula (I) selected from the group of(3-Aminopropyl)triethoxysilane (3-Aminopropyl)trimethoxysilane1-(3-Aminopropyl)silantriol (2-Aminoethyl)triethoxysilane(2-Aminoethyl)trimethoxysilane 1-(2-Aminoethyl)silantriol(3-Dimethylaminopropyl)triethoxysilane(3-Dimethylaminopropyl)trimethoxysilane1-(3-Dimethylaminopropyl)silantriol(2-Dimethylaminoethyl)triethoxysilane(2-Dimethylaminoethyl)trimethoxysilane and/or1-(2-Dimethylaminoethyl)silantriol.
 5. The process according to claim 1,wherein the agent (a) comprises at least one organic silicon compound(a1) of formula (II).(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)—Si(R₆′)_(d′)(OR₅′)_(c′)  (II),where e and f both stand for the number 1, g and h both stand for 0, Aand A′ independently represent a linear, divalent C₁-C₆ alkylene groupand R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethylgroup, a 2-alkenyl group, a 2-aminoethyl group or a group of formula(III).
 6. The process according to claim 1, wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (II)selected from the group of3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamineN-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamineN-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol2-[bis[3-(triethoxysilyl)propyl]amino]ethanol3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamineN1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/orN,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.
 7. The processaccording to claim 1, wherein the agent (a) comprises at least oneorganic silicon compound (a1) of formula (IV).R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV), where R₉ represents a C₁-C₁₂ alkyl group,R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group, Ru represents aC₁-C₆ alkyl group k is an integer from 1 to 3, and m stands for theinteger 3−k.
 8. The process according to claim 1, wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (IV)selected from the group of Methyltrimethoxysilane MethyltriethoxysilaneEthyltrimethoxysilane Ethyltriethoxysilane OctyltrimethoxysilaneOctyltriethoxysilane Dodecyltrimethoxysilane and/orDodecyltriethoxysilane.
 9. (canceled)
 10. Process according to claim 1,wherein the agent (a)—based on the total weight of agent (a)—comprises:from about 0.5 to about 3.0% by weight of at least one first organicsilicone compound (a1) selected from the group of(3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,(2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane,(3-dimethylaminopropyl)trimethoxysilane,(3-dimethylaminopropyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane and(2-dimethylaminoethyl)triethoxysilane, and from about 3.2 to about 10.0%by weight of at least one second organic silicon compound (a1) selectedfrom the group of methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, octyltrimethoxysilane,octyltriethoxysilane, dodecyltrimethoxysilane anddodecyltriethoxysilane.
 11. (canceled)
 12. The method according to claim1, wherein the agent (a) is at least one coloring compound (a2) from thegroup of inorganic pigments selected from the group of colored metaloxides, metal hydroxides, metal oxide hydrates, silicates, metalsulfides, complex metal cyanides, metal sulfates, bronze pigments and/orcolored pigments based on mica or mica coated with at least one metaloxide and/or a metal oxychloride.
 13. (canceled)
 14. The methodaccording to claim 1, wherein the agent (a) is at least one coloringcompound (a2) selected from the group of anionic, nonionic and/orcationic direct dyes.
 15. (canceled)
 16. (canceled)
 17. (canceled) 18.The method according to claim 1, wherein the agent comprises (a): (a3)at least one alkoxy-modified and/or amino-modified silicone polymer. 19.The method according to claim 1, wherein the agent comprises (a): (a3)at least one silicone polymer comprising at least one structural unit offormula (S-I)

wherein n is an integer from about 2 to about
 20. 20. The methodaccording to claim 1, wherein the agent comprises (a): (a3) at least onesilicone polymer comprising at least one structural unit of the formula(S-XIII)


21. The method according to claim 1, wherein the agent (b) is at leastone film-forming polymer (b1) chosen from the group of the homopolymersor copolymers of acrylic acid, the homopolymers or copolymers ofmethacrylic acid, the homopolymers or copolymers of acrylic acid esters,the homopolymers or copolymers of methacrylic acid esters, thehomopolymers or copolymers of acrylic acid amides, the homopolymers orcopolymers of methacrylic acid amides of homopolymers or copolymers ofvinylpyrrolidone, of homopolymers or copolymers of vinyl alcohol, ofhomopolymers or copolymers of vinyl acetate, of homopolymers orcopolymers of ethylene, of homopolymers or copolymers of propylene, ofhomopolymers or copolymers of styrene, of polyurethanes, of polyestersand/or of polyamides.
 22. The process according to claim 1, wherein theagent (b) comprises at least one film-forming polymer (b1) comprising atleast one structural unit of the formula (P-I) and at least onestructural unit of the formula (P-II)

where M is a hydrogen atom or ammonium (NH4), sodium, potassium, ½magnesium or ½ calcium.
 23. Process according to claim 1, wherein theagent (b) comprises—based on the total weight of the agent (b)—one ormore film-forming polymers (b1) in a total amount of from about 0.1 toabout 8.0% by weight.
 24. The process according to claim 1, whereinfirst the agent (a) is applied, then the agent (b) is applied, theperiod between the application of the agents (a) and (b) being at mostabout 24 hours.
 25. The process according to claim 1, comprising thefollowing steps in the order indicated (1) applying agent (a) on thekeratinous material, (2) allowing the agent (a) to act for a period offrom about 10 seconds to about 10 minutes, (3) optionally, rinsing thekeratinous material with water, (4) applying agent (b) on the keratinousmaterial, (5) allowing the agent (b) to act for a period of from about30 seconds to about 30 minutes, (6) optionally, rinsing the keratinousmaterial with water.
 26. Kit-of-parts for dyeing keratinous material,comprising separately packaged a first container comprising an agent(a′), wherein the agent comprises (a′): (a1) at least one organicsilicon compound selected from the group of silanes having one, two orthree silicon atoms, and a second container comprising an agent (a″),wherein the agent comprises (a″): (a2) at least one colorant compoundselected from the group of pigments and/or direct dyes, and a thirdcontainer comprising an agent (b), wherein the agent comprises (b): (b1)at least one film-forming polymer, wherein the components (a1), (a2),and (b1) are defined in claim 1.